Colorant compounds containing copolymerizable vinyl groups

ABSTRACT

Disclosed are novel colorant compounds which contain one or more ethylenically-unsaturated (vinyl), photopolymerizable radicals which may be copolymewrized (or cured) with ethylenically-unsaturated monomers to produce colored compositions such as colored acrylic coatings and polymers, e.g., coatings and polymers produced from acrylate and methacrylate esters, colored polystyrenes, and similar colored polymeric materials derived from other ethylenically-unsaturated monomers. The present invention also pertains to processes for the preparation of certain of the photopolymerizable colorant compounds.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application Ser.No. 60/223,521, filed Aug. 7, 2000.

FIELD OF THE INVENTION

This invention pertains to certain novel colorant compounds whichcontain one or more ethylenically-unsaturated (vinyl),photopolymerizable radicals which may be copolymerized (or cured) withethylenically-unsaturated monomers to produce colored compositions suchas colored acrylic polymers, e.g., polymers produced from acrylate andmethacrylate esters, colored polystyrenes, and similar colored polymericmaterials derived from other ethylenically-unsaturated monomers. Thepresent invention also pertains to processes for preparing certain ofthe photopolymerizable colorant compounds.

BACKGROUND AND PRIOR ART

It is known (J.S.D.C., April 1977, pp 114-125) to produce coloredpolymeric materials by combining a reactive polymer such terepolymershaving epoxy groups or polyacryloyl chloride with anthraquinone dyescontaining nucleophilic reactive groups such as amino or hydroxy groups;to graft acryloylaminoanthraquinone dyes to the backbone of vinyl ordivinyl polymers; and to polymerize anthraquinone dyes containingcertain olefinic groups to produce polymeric dyes/pigments. U.S. Pat.No. 4,115,056 describes the preparation of blue, substituted1,4-diaminoanthraquinone dyes containing one acryloyloxy group and andthe use of the dyes in coloring various fibers, especially polyamidefibers. U.S. Pat. No. 4,943,617 discloses liquid crystalline copolymerscontaining certain blue, substituted1,5-diamino-4,8-dihydroxyanthraquinone dyes containing an olefinic groupcopolymerized therein to provide liquid crystal copolymers having highdichromism. U.S. Pat. No. 5,055,602 describes the preparation of certainsubstituted 1,4-diaminoanthraquinone dyes containing polymerizableacryloyl and methacryloyl groups and their use in coloring polyacrylatecontact lens materials by copolymerizing.

U.S. Pat. No. 5,362,812 discloses the conversion of a variety of dyeclasses, including anthraquinones, into polymeric dyes by (a)polymerizing 2-alkenylazlactones and reacting the polymer with dyescontaining nucleophilic groups and by (b) reacting a nucleophilic dyewith an alkenylazlactone and then polymerizing the free radicallypolymerizable dyes thus produced. The polymeric dyes are reported to beuseful for photoresist systems and for colorproofing. U.S. Pat. No.5,367,039 discloses a process for preparing colored vinyl polymerssuitable for inks, paints, toners and the like by emulsionpolymerization of a vinyl monomer with reactive anthraquinone dyesprepared by functionalizing certain anthraquinone dyes with methacryloylgroups.

The preparation of a variety of dyes, including some anthraquinones,which contain photopolymerizable groups and their use for color filterssuitable for use in liquid crystal television sets, color copyingmachines, photosensitive resist resin compositions, and the like aredescribed in U.S. Pat. No. 5,578,419.

BRIEF SUMMARY OF THE INVENTION

The first embodiment of the present invention concerns colorantcompounds having Formulas I and II:

wherein

-   -   A, is a mono-, di-, tri- or tetravalent chromophore;    -   X is —R₁-O-Q or the phtopolymerizable group        —CH₂—C₆H₄-p-C(R₂)═CH₂;    -   Y is —R₁—O-Q, —CH₂—C₆H₄-p-C(R₂)═CH₂ or Q;    -   R is selected from hydrogen, C₁-C₆ alkyl, aryl and C₃-C₈        cycloalkyl;    -   R₁ is selected from C₂-C₈ alkylene, —(—CH₂CH₂O—)_(m)—CH₂CH₂— and        1,4-cyclohexylenedimethylene;    -   R₂ is selected from hydrogen and C₁-C₆ alkyl;

-   n is 1 to 4;    -   m is 1-3;    -   Q is a photopolymerizable group selected from an organic radical        having the formulae:        wherein    -   R₃ is selected from hydrogen or C₁-C₆ alkyl;    -   R₄ is selected from hydrogen; C₁-C₆ alkyl; phenyl; phenyl        substituted with one or more groups selected from C₁-C₆ alkyl,        C₁-C₆ alkoxy, —N(C₁-C₆ alkyl)₂, nitro, cyano, C₂-C₆        alkoxycarbonyl, C₂-C₆ alkanoyloxy and halogen; 1- and        2-naphthyl; 1- and 2-naphthyl substituted with C₁-C₆ alkyl or        C₁-C₆ alkoxy; 2- and 3-thienyl; 2- and 3-thienyl substituted        with C₁-C₆ alkyl or halogen; 2- and 3-furyl; and 2- and 3-furyl        substituted with C₁-C₆ alkyl;    -   R₅ and R₆ are independently selected from hydrogen, C₁-C₆ alkyl,        substituted C₁-C₆ alkyl; aryl; or R₅ and R₆ may be combined to        represent a —(—CH₂—)₃₋₅— radical;    -   R₇ is selected from hydrogen or a group selected from C₁-C₆        alkyl, substituted C₁-C₆ alkyl, C₃-C₈ alkenyl, C₃-C₈ cycloalkyl        and aryl; and    -   R₈ is selected from hydrogen, C₁-C₆ alkyl and aryl. The colorant        compounds have good color strength, good solubility in the        reactive monomers and good light-fastness. Certain of the        colorant compounds exhibit outstanding thermal stability.

A second embodiment of the present invention concerns a process forpreparing photopolymerizable colorants having Formula I, wherein X is ap-vinylbenzyl radical having the formula —CH₂—C₆H₄-p-C(R₂)═CH₂ whichcomprises reacting colored acidic compounds having the structure:

with the compounds having the structure ClCH₂—C₆H₄-p-C(R₂)═CH₂ in thepresence of base, wherein A, R₂ and n are as defined previously.

A third embodiment of the present invention concerns a process forpreparing photopolymerization colorants having Formula II, wherein Y isa p-vinylbenzyl radical having the formula —CH₂—C₆H₄-p-C(R₂)═CH₂ whichcomprises reacting colored acidic compounds having the structure

with 4-chloromethylstyrene compounds having the structureClCH₂—C₆H₄-p-C(R₂)═CH₂ in the presence of a base, wherein A, R, R₂ and nare defined above.

A fourth embodiment of the invention concerns a process for preparingcolored photopolymerizable compounds having Formula I and Formula II,respectively, wherein X and Y are —CH₂CH₂—O-Q or —CH₂CH(CH₃)—O-Q, whichcomprises the steps of

-   (a) reacting a colored acidic compounds having the structures:    respectively, with at least about n molecular equivalents of    ethylene or propylene carbonate for each molecular equivalent of    acidic compounds to produce the 2-hydroxyalkyl derivatives of said    acidic compounds followed by:-   (b) reaction of said colored hydroxyalkyl derivatives with about n    molecular equivalents of one or more acylating agents having the    structures    CICOC(R₃)═CH—R₄ or O[COC(R₃)═CH—R₄]₂,  Ib    O═C═N—COC(R₃)═CH—R₄,  IIb    O═C═N—C₁-C₆ alkylene OCOC(R₃)═CH—R₄,  IIIb    wherein A, n, Q, R, R₃, R₄, R₅, R₆, R₈ are defined previously.

A fifth embodiment of the present invention concerns a process forpreparing compounds of Structure II, wherein Y is a photopolymerizablegroup Q which comprises reacting colored acidic compounds having thestructure:

with at least about n molecular equivalents of one or more acylatingagents Ib through IXb described above wherein A, R, n and Q are definedabove.

A sixth embodiment of the present invention pertains to a coatingcomposition comprising (i) one or more polymerizable vinyl compounds,(ii) one or more of the colorant compounds having Formulas I and IIdescribed above, and (iii) a photoinitiator. A seventh embodiment of thepresent invention pertains to a polymeric composition, typically acoating, comprising a polymer of one or more acrylic acid esters, one ormore methacrylic acid esters and/or other polymerizable vinyl compounds,having copolymerized therein one or more of the colorant compoundshaving Formulas I and II described above.

DETAILED DESCRIPTION

In formulas I and II, A represents a mono-, di-, tri- or tetravalentresidue of a chromophore, i.e., a colored compound, including residueswhich in combination with —CO₂X produces a chromophore. Examples of thechromophoric residues which A may represent include anthraquinone,anthrapyridone (3H-dibenz-[f, ij]-isoquinoline-2,7-dione,anthrapyrimidine (7H-dibenz-[f,ij]-isoquinoline-7-one), anthrapyrimidine(7H-benzo[e]-perimidine-7-one), anthrapyrimidone, isothiazoloanthrone,azo, bis-azo, methine, bis-methine, coumarin (2-H-1-benzopyran-2-one),3-aryl-2,5-dioxypyrroline, 3-aryl-5-dicyanomethylene-2-oxypyrroline,perinone, quinophthalone, phthalocyanine, metal phthalocyanine,nitroarylamine or a 2,5-diarylaminoterephthalic ester chromophore.

The terms “C₁-C₆-alkyl” and “C₁-C₈-alkyl” are used herein to denote astraight- or branched-chain, saturated, aliphatic hydrocarbon radicalcontaining one to six, and one to eight, carbon atoms. The term“substituted C₁-C₆-alkyl” is used to denote a C₁-C₆-alkyl groupsubstituted with one or more groups, preferably one to three groups,selected from the group consisting of hydroxy, halogen, cyano, aryl,aryloxy, arylthio, C₁-C₆ alkylthio, C₃-C₈-cycloalkyl, C₂-C₆-alkanoyloxyand —(—O—R₉—)_(p)—R₁₀ wherein R₉ is selected from the group consistingof C₁-C₆ alkylene, C₁-C₆-alkylene-arylene, cyclohexylene, arylene,C₁-C₆-alkylene-cyclohexylene andC₁-C₆-alkylene-cyclohexylene-C₁-C₆-alkylene, R₁₀ is selected from thegroup consisting of hydrogen, hydroxy, carboxy, C₂-C₆-alkanoyloxy,C₂-C₆-alkoxycarbonyl, aryl and C₃-C₈-cycloalkyl; and p is 1, 2, or 3.

The terms “C₁-C₆-alkylene”, “C₂-C₄-alkylene” and “C₂-C₈-alkylene” areused to denote straight- or branched-chain, divalent, aliphatichydrocarbon radicals containing one to six, two to four, and two toeight carbons, respectively. These divalent radicals may be substitutedwith one to three groups selected from C₁-C₆-alkoxy,C₂-C₆-alkoxycarbonyl, C₂-C₆-alkanoyloxy, hydroxy, aryl and halogen. Theterm “C₃ C₈-alkenyl” is used to denote an aliphatic hydrocarbon radicalcontaining at least one double bond. The term “C₃-C₈-alkynyl” is used todenote an aliphatic hydrocarbon radical containing at least one triplebond and three to eight carbon atoms. The term “C₃-C₈-cycloalkyl” isused to denote a saturated, carbocyclic, hydrocarbon radical havingthree to eight carbon optionally substituted with one to threeC₁-C₆-alkyl group(s). The term “C₃-C₈-cycloalkylene” is used to denote adivalent, carbocyclic hydrocarbon radical which contains three to eightcarbon atoms, preferably five or six carbons.

The term “aryl” as used herein denotes phenyl and phenyl substitutedwith one to three substituents selected from C₁-C₆-alkyl, substitutedC₁-C₆-alkyl, C₁-C₆-alkoxy, halogen, carboxy, cyano, C₂-C₆-alkanoyloxy,C₁-C₆-alkylthio, C₁-C₆-alkylsulfonyl, trifluoromethyl, hydroxy,optionally substituted sulfamoyl, C₂-C₆-alkoxycarbonyl,C₂-C₆-alkanoyl-amino and —O—R₁₁, S—R₁₁, —SO₂—R₁₁, —NHSO₂R₁₁ and—NHCO₂R₁₁, wherein R₁₁ is phenyl or phenyl substituted with one to threegroups selected from C₁-C₆-alkyl, C₁-C₆-alkoxy and halogen. The term“arylene” as used herein denotes includes 1,2-, 1,3- and 1,4-phenyleneand such divalent radicals substituted with one to three groups selectedfrom C₁-C₆-alkyl, C₁-C₆-alkoxy and halogen.

The term “halogen” is used to include fluorine, chlorine, bromine, andiodine. The term “optionally substituted sulfamoyl” is used to describethe group having the structure —SO₂N(R₁₂)R₁₃, wherein R₁₂ and R₁₃ areindependently selected from hydrogen, C₁-C₆-alkyl, substitutedC₁-C₆-alkyl, C₃-C₈-alkenyl, C₃-C₈-cycloalkyl, aryl and heteroaryl.

The terms “C₁-C₆-alkoxy”, “C₂-C₆-alkoxycarbonyl”, “C₂-C₆-alkanoyl”,“C₂-C₆-alkanoyloxy” and “C₂-C₆-alkanoylamino” are used to denoteradicals corresponding to the structures —OR₁₄, —CO₂ R₁₄, —COR₁₄,—OCOR₁₄ and NHCOR₁₄, respectively, wherein R₁₄ is C₁-C₆-alkyl orsubstituted C₁-C₆-alkyl. The term “heteroaryl” as used herein denotes a5- or 6-membered aromatic ring containing one to three hetero atomselected from oxygen, sulfur and nitrogen. Examples of such heteroarylgroups are thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl,isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl,oxadiazolyl, tetrazolyl, pyridyl, pyrimidyl, benzoxazolyl,benothiazolyl, benzimidazolyl, indolyl and the like and these optionallysubstituted with one to three groups selected from C₁-C₆-alkyl,C₁-C₆-alkoxy, substituted C₁-C₆-alkyl, halogen, C₁-C₆-alkylthio, aryl,arylthio, aryloxy, C₂-C₆-alkoxycarbonyl and C₂-C₆-alkanoylamino.

The preferred azo dyes of the invention encompassed by Formula I havethe following general Formula XIII:D-N═N-Z  XIIIwherein D is the residue of an aromatic or heteroaromatic, diazotizableamine which has been diazotized and coupled with an electron richcoupling component H-Z and is preferably derived from the aromatic andheteroaromatic classes of unsubstituted and substituted anilines,1-naphthylamines, 1-aminoanthraquinones, 4-aminoazobenzenes,2-aminothiazoles, 2-aminobenzothiazoles, 3-amino-2,1-benzisothiazoles,2-aminothieno [2,3-d]thiazoles, 5-aminopyrazoles,4-aminopyrazoloiso-thiazoles, 2-amino-1,3,4-thiadiazoles,5-amino-1,2,3-thiadiazoles, 5-amino-1,2,3-triazoles,2-amino-1,3,4-triazoles, 2(5) aminoimidazoles, 3-amino-pyridines,2(3)aminothiophenes, 2(3)aminobenzo [5]thiophenes,2-amino-thieno[3,2-5]thiophenes, 3-aminothieno[2,3]-isothiazoles,3-amino-7-benz-2,1-isothiazoles, 3-aminoisothiazolo[3,4-d]pyridines,3(4)-aminophthal-imides and 5(6)amino-1,2-benzisothiazolon-1,1-dioxides; wherein the substituuents whichare present on D are selected from C₁-C₆-alkyl; C₁-C₆-alkoxy;C₃-C₈-cycloalkyl; halogen; C₂-C₆-alkoxycarbonyl;

C₂-C₆-alkanoyloxy; formyl; C₂-C₆-alkanoyl; dicyanovinyl; thiocyano;trifluoro-methyl; trifluoroacetyl; cyano; carbamoyl; —CONHCl-C₆-alkyl;—CON(C₁-C₆-alkyl)₂; —CONH aryl; sulfamoyl; —SO₂NHC₁-C₆-alkyl;—SO₂N(C₁-C₆-alkyl)₂; —SO₂NHaryl; —SO₂NHC₃-C₈-cycloalkyl;—CONHC₃-C₈-cycloalkyl; aryl; aroyl; heteroaryl; NHSO₂C₁-C₆ alkyl;N(C₁-C₆-alkyl) SO₂C₁-C₆-alkyl; NHSO₂ aryl; NHCO₂C₁-C₆-alkyl; NHCONHC₁-C₆-alkyl; NHCONH aryl; —N—(C₁-C₆-alkyl)-aryl; arylazo; aryloxy;arylthio; C₃-C₈-cycloalkoxy; heteroarylazo; heteroaryl-thio;arylsulfonyl; tricyanovinyl; aryloxysulfonyl; C₁-C₆-alkylsulfonyl;fluorosulfonyl; trifluoromethylsulfonyl; hydroxy; nitro and —CH=AM,wherein AM is the residue of an active methylene compound; —CO₂X and

wherein -L- is a linking group selected from —O—, —S— and —SO₂— and X isas defined previously; Z is the residue of an electron rich couplingcomponent selected from the classes of anilines,1,2,3,4-tetrahydro-quinolines,aminonaphthylamines, benzomorpholines(3,4-dihydro-2H-1,4-benzoxazines), pyrazolones, pyrazoles,3-cyano-6-hydroxy-2-pyridones, 2,3-dihydroindoles, indoles,4-hydroxycoumarins, 4-hydroxy-2-quinolones, imidazo[2,1-b]-thiazoles,2,6-diamino-3-cyanopyridines; 5,5-dimethyl-1,3-cyclohexanedione(dimedone), phenols, naphthols and 2,4-pentanediones; wherein the azocompounds of Formula XIII contain a total of from one to fourphotopolymerizable groups (—CO₂X), wherein said group(s) may bepositioned on moiety D and/or moiety Z.

Another group of preferred azo dye of the invention encompassed byFormula II have the general Formula XIV:D₁-N═N-Z₁  XIVwherein D₁ is the residue of an aromatic or hereroaromatic amine whichhas been diazotized and coupled with an electron rich coupling componentHZ₁, wherein D₁ is derived from the same optionally substituted aromaticamines and heteroaromanic amines as described for Formula XIII above,except that the photopolymerizable group which may be present on D₁, isa triazolyl radical having the formula:

instead of —CO₂X or

and wherein R and Y are as previously defined; Z₁ is the residue of acoupling component selected from the same classes as described above forZ in Formula XIII and which may be substituted with the group

with the provision that the azo compounds of Formula XIV contain a totalof from one to four photopolymerizable groups

wherein said groups(s) may be positioned on moiety D₁ and/or moiety Z₁.

Typical coupler residues represented by Z above in Formula XIII includethe groups having the structures:

wherein R₁₅ is hydrogen or 1-2 groups selected from C₁-C₆-alkyl,C₁-C₆-alkoxy, halogen, NHCOR₂₂, NHCO₂R₂₂, NHCON(R₂₂) R₂₃ and NHSO₂R₂₃,wherein R₂₂ is selected from hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl andaryl, R₂₃ is selected from C₁-Cs-alkyl, C₃-C₈-cycloalkyl and aryl,wherein each C₁-C₆ alkyl group in R₂₂ and R₂₃ may be further substitutedwith one or more groups selected from C₁-C₆-alkoxy, hydroxy,C₃-C₈-cycloalkyl, aryl, aryloxy, arylthio, cyano, succinimido, —CO₂X,

wherein —CO₂X is a photopolymerizable group as described above; L₁ isselected from a covalent bond, —O—, —S—, —SO₂—, —CO₂—, —SO₂NH—, —CONH—and —SO₂N(C₁-C₆-alkyl)- ; wherein each aryl group in R₂₂ and R₂₃ in thedefinition of R₁₅ may be substituted with at least onephotopolymerizable —CO₂X group; wherein R₂₄ represents hydrogen or 1-2groups selected from —CO₂X, C₁-C₆-alkyl, C₁-C₆-alkoxy and halogen; R₁₆and R₁₇ are independently selected from hydrogen; C₃-C₈-cycloalkyl;C₃-C₈-alkenyl; C₃-C₈-alkynyl; C₁-C₆-alkyl and C₁-C₆-alkyl substitutedwith one or more groups selected from —CO₂X,

C₃-C₈-cycloalkyl, aryl, hydroxy, cyano, —OC₂H₄OH, —SCH₂CH₂OH, halogen,—OC₁-C₆-alkyl, —S C₁-C₆-alkyl, —O aryl, —S aryl, —SO₂ aryl,—SO₂C₁-C₆-alkyl, —S heteroaryl, 2-pyrrolidino, phthalimidino,phthalimdo, succinimido, glutar-imido, o-benzoic sulfimido,—NHCOC₁-C₆-alkyl, —NHCOH, —NHSO₂ C₁-C₆-alkyl, —NHSO₂aryl, —NHCOaryl,—NHCO₂C₁-C₆-alkyl, —SO₂NH₂, —CONH₂, —SO₂NH—C₁-C₆-alkyl,—SO₂N(C₁-C₆-alkyl)₂, —CO₂C₁-C₆-alkyl, —CONH C₁-C₆-alkyl, —CO₂-aryl,—CON—(C₁-C₆-alkyl)₂, —CONH-aryl, —CON—(C₁-C₆-alkyl)aryl,—SO₂N(C₁-C₆-alkyl)aryl, —OCOC₁-C₆-alkyl, —OCOaryl, —OCO₂C₁-C₆-alkyl;groups of the formulae:

wherein Y₂ is selected from 1,2-phenylene; 1,2-phenylene substitutedwith C₁-C₆ alkyl, C₁-C₆-alkoxy, halogen, CO₂C₁-C₆-alkyl or nitro; C₂-C₄alkylene; —OCH₂—; —SCH₂—; —CH₂OCH₂—; —CH₂SCH₂—; —NHCH₂—;—NHCH₂CH₂—N(C₁-C₆-alkyl)CH₂—; —N(C₁-C₆-alkyl)CH₂CH₂; —NHC(aryl)₂, andwherein R₁₆ and R₁₇ may be combined with themselves or another elementto which they are attached to form a radical Z having the formula:

wherein L₃ is selected from a covalent bond, —O—, —S—, —CH₂—, —SO₂—,—N(COC₁-C₆-alkyl)-, —N(SO₂C₁-C₆-alkyl)-, —N(COaryl)- and —N(SO₂aryl)-;R₁₈, R₁₉ and R₂₀ are independently selected from hydrogen andC₁-C₆-alkyl; R₂₁ is selected from hydrogen, C₁-C₆-alkyl and aryl.

Typical coupler residue represented by Z₁ is Formula XIV include thosementioned immediately above Z except that the photopolymerizable groupwhich may be present as a substituent or on R₁₅, R₁₆, R₁₇, R₂₂, or R₂₃is the triazolyl group having the formula:

instead of those listed.

The preferred methine, bis-methine, 3-aryl-2,5-dioxypyrroline,3-aryl-5-dicyanomethylene-2-oxypyrroline and coumarin compounds ofFormula I have the following general Formulas XV, XVI, XVII, XVIII andXIX respectively;

wherein R₂₅ is an electron rich aromatic residue selected from thefollowing:

wherein R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ are as defined for Z previouslyin Formula XIII; wherein R₁₆′ is selected from the same groups as R₁₆;wherein R₂₆ is selected from cyano, C₁-C₆-alkoxycarbonyl,C₁-C₆-alkylsulfonyl, arylsulfonyl, aryl, heteroaryl, formyl,C₁-C₆-alkanoyl or —CH=AM; wherein R₂₇ is hydrogen or cyano; wherein AMis the residue of an active methylene compound selected frommalononitrile, α-cyanoaceticacid esters, malonic acid esters,α-cyanoacetic acid amides, α-C₁-C₆-alkylsulfonyl-acetonitriles,α-arylsulfonylacetonitriles, α-C₁-C₆-alkanoylacetonitriles,α-arylsulfonyl-acetonitriles, α-C₁-C₆-alkanoylacetonitriles,α-arylacetonitriles, α-herero-acylacetonitriles, bis(heteroaryl)methanes, 1,3-indanediones, 2-furanones, benzo-2-furanones, benzo (b)thieno-3-xlidene propanedinitrile-5,5-dioxides,1,3-bis(dicyanomethylene)indanes, barbituric acid, 5-pyrazolones,dimedone, 3-oxo-2,3-dihydro-1-benzothiophene-1,1-dioxides, arylC(CH₃)═C(CN)₂ and NC CH₂ CO₂X, R₂₈; wherein —CO₂X is aphotopolymerizable group as previouly defined.

Examples of the anthraquinone (Formulas XX α-e), anthrapyridone(3H-dibenz-[f,ij]-isoquinoline-2-7-dione) (Formulas XXI a-e) andanthrapyridine (7H-dibenz-[f, ij]-isoquinoline-7-one) (Formulas XXIIa-e) colorants include the compounds having the structures set forthbelow:

wherein R₂₈ is hydrogen or represents 1-4 groups selected from amino;C₁-C₈-alkylamino; C₁-C₈-alkylamino substituted with onelor more groupsselected from hydroxy, cyano, halogen, aryl, heteroaryl,C₃-C₈-cycloalkyl, furyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, arylthio,aryloxy, —(OCH₂CH₂—)₁₋₃OR′, wherein R′ is selected from hydrogen,C₁-C₆-alkyl and C₂-C₆-alkanoyloxy; C₃-C₈-cycloalkylamino;C₃-C₈-alkenylamino; C₃-C₈-alkynylamino; arylamino; furfurylamino;C₁-C₆-alkoxy; —(OCH₂CH₂—)₁₋₃OR′, wherein R′ is as defined previously;halogen; hydroxy; C₁-C₆-alkylthio; arylthio; aryl; aryloxy; arylsulfonylC₂-C₆-alkanoyl; aroyl; C₂-C₆-alkanoyloxy; C₂-C₆-alkoxycarbonyl;heteroaryl; heteroarylthio; cyano; nitro; trifluoromethyl; thiocyano;—SO₂C₁-C₆-alkyl; —SO₂NH₂; —SO₂NHC₁-C₆-alkyl; —SO₂N(C₁-C₆alkyl)₂;—SO₂N(C₁-C₆alkyl)aryl; —SO₂NHaryl; —CONH₂; CONHCl-C₆-alkyl;—CON(C₁-C₆-alkyl)₂; —CONHaryl; —CON(C₁-C₆-alkyl)aryl; C₁-C₆-alkyl;tetrahydrofurfurylamino; 4-(hydroxymethyl)cyclohexylmethylamino; and

-   R₂₉ is hydrogen or 1-2 groups selected from C₁-C₆-alkyl, halogen and    C₁-C₆-alkoxy; R₃₀ is selected from hydrogen, C₁-C₈-alkyl,    substituted C₁-C₈-alkyl as defined previously in the definition of    R₂₈, aryl and C₃-C₈-cycloalkyl; R₃₁ is selected from hydrogen,    cyano, C₁-C₆-alkoxy, C₁-C₆-alkylthio, aryl, aryloxy, arylamino,    arylthio, heteroaryl, heteroarylthio, halogen, C₂-C₆-alkoxycarbonyl,    aroyl; C₁-C₆-alkylsulfonyl, arylsulfonyl and C₁-C₆-alkyl-amino; R₃₂    is selected from hydrogen, C₁-C₆-alkyl, aryl and —N(R₃₃)R₃₄, wherein    R₃₃ and R₃₄ are independently selected from hydrogen; C₁-C₆-alkyl;    C₁-C₆-alkyl substituted with C₂-C₆-alkanoyloxy, aryl and    C₃-C₈-cycloalkyl; aryl; C₃-C₈-cycloalkyl; wherein R₃₃ and R₃₄ may be    combined to produce divalent radicals such as —(CH₂)-4-6 and    —CH₂CH₂-L₆-CH₂CH₂—, wherein L₆ is selected from —O—, —S—, —SO₂— and    —N(R₃₄)—, wherein R₃₄′ is selected from hydrogen, C₁-C₆-alkyl, aryl,    aroyl, C₁-C₆— alkanoyl, C₁-C₆-alkylsulfonyl and aryl-sulfonyl; L₄    and L₅ are selected from —O—, —S—, —SO₂—, —CON(R₃₃)— and    —SO₂N(R₃₃)—.

Some of the preferred colorants encompassed by Formula I wherein A is aquinophthalone chromophore have the following Formula XXIII:

wherein R₃₅ is selected from hydrogen, bromine, arylthio,heteroarylthio, arylsulfonyl,

wherein X and R₂₄ are as defined above.

Some of the preferred nitroarylamine colorants encompassed by Formula Iwherein A is a nitroarylamine chromophore have the following Formula(XXIV):

wherein R₃₆ is selected from hydrogen, halogen, C₁-C₆-alkyl andC₁-C₆-alkoxy; R₃₇ and R₃₈ are independently selected from hydrogen;C₁-C₆-alkyl; C₃-C₆-cycloalkyl; C₃-C₈-cycloalkyl; C₃-C₈-cycloalkyl,C₂-C₆-alkanoyloxy; aryl and

Some of the preferred colorants encompassed by Formula I wherein A is aperinone chromophore correspond to Formulae XXV-XXIX:

wherein R₃₉ is hydrogen or 1-4 groups selected from C₁-C₆-alkyl,C₁-C₆-alkoxy, amino, CO₂X, C₁-C₆-alkylamino, C₃-C₈-cycloalkylamino,arylamino, arylthio, hereroarylthio and

wherein L₇ is selected from —S—, —O— and —NH—, with the provision thatone to four —CO₂X groups be present.

Preferred colorants of Formula I containing the 2,5-diarylaminoterephthalate chromophore have Formula XXX

wherein R₄₀ is hydrogen or —CO₂X or represents 1-3 groups selected fromC₁-C₆-alkyl, C₁-C₆-alkoxy, halogen, and —NHC₂-C₆-alkanoylamino.

The preferred photopolymerizable colorant compounds of the presentinvention are those of Structures I and II where X and Y, respectively,are selected from —CH₂CH₂OQ, —CH₂CH(CH₃)OQ, —(CH₂CH₂O)₂₋₃—CH₂CH₂OQ,—CH₂C(CH₃)₂CH₂OQ, and —CH₂—C₆H₁₀—CH₂OQ and A is an anthraquinone,anthrapyridone or 2,5-diarylaminoterephthalate chromophore residue.

The photopolymerizable colorants having Formula I and II where X and Yare the photopolymerizable p-vinylbenzyl groups radical having theformula —CH₂—C₆H₄-p-C(R₂)═CH₂ are prepared in general by reactingcolored acidic compounds having Formulae III and IV with a4-chloro-methylstyreneV, respectively, as follows:

wherein A, n, R and R₂ are as defined previously, to produce coloredcompounds VI and VII. The reactions of the colored acidic compoundshaving Formulae III and IV with the 4-chloromethylstyrenes V are carriedout in the presence of a polar aprotic solvent such asN,N-dimethylform-amide (DMF), N-methyl-2-pyrrolidinone (NMP),N,N-dimethylacetamide (DMAC), sulfolane, etc. in the presence of one ormore bases such as an alkali metal carbonate, an alkali metalbicarbonate, a trialkylamine, a cyclic nitrogen compounds such as1,8-diazabicyclo [5.4.0]undec-7-ene (PBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), and the like. The reaction may under somereaction conditions be facilitated by the presence of a catalytic amountof an alkali metal bromide, alkali metal iodide and/or a conventionalphase transfer catalysts, e.g., a tetraalkylammonium halide such as achloride or bromide. The reactions are usually carried out between about50° C. to about 150° C., preferably from about 90° C. to about 125° C.

The photopolymerizable dyes having Formulae I and II, where X and Y are—R₁-O-Q are, in general, prepared by first reacting colored acidicacidic compounds having Formulae III and IV with an alkylating agentcontaining one or more hydroxy groups having Formula VIII as follows:

wherein A, n, R and R₁ are as defined previously and Z is halogen, toproduce an intermediate hydroxy compound IX and X. Reaction conditionsused for preparing compounds IX and X are those described in thepreparation of VI and VII above. Although intermediate hydroxy compoundsIX and X where R₁ is —CH₂CH₂— or —CH₂CH(CH₃)— may be prepared asdescribed above by using the corresponding 2-bromo- or chloro-alkanol,the preferred route uses ethylene or propylene carbonate which avoidsthe use of toxic haloalkanols according to the following equations:

wherein R′ is hydrogen or methyl, to produce hydroxyalkyl derivatives XIand XII. These reactions are facilitated by the presence of catalyticamounts of alkali halides, teraalkylammonium halides ortetraalkyl-ammonium hydroxides. The reactions may be carried out byheating the intermediate colored diacids III and IV with at least molarequivalent amounts of alkylene carbonate. Excess alkylene carbonate alsomay be useful as the solvent or a co-solvent for the reaction. Inparticular, ethylene and propylene glycol have been found to beeffective co-solvents for the preparation of XI and XII. Compounds IXand X (or XI and XII) are then acylated with one of acylating agents lbthrough IXb described above to introduce the desired Q groups to preparephotopolymerizable compounds having Formulae I and II. Q groups Ia-IXaare introduced by reacting hydroxy compounds IX and X with acylatingagents Ib-IXb, respectively.

Intermediate colored acidic compounds III and IV are disclosed in U.S.Pat. Nos. 3,689,501; 3,816,392; 4,359,570; 4,403,092; 4,617,373;4,740,581; 4,745,173; 4,804,719; 4,892,922; 5,030,708; 5,102,980;5,194,571; 5,274,072; 5,281,659; 5,372,864; 5,962,557 and WO 98/23690,wherein particularly useful diacidic intermediate colorants aredisclosed.

The azo dyes above which correspond to Formula XIII and Formula XIV maybe prepared by reacting azo dyes containing one to four carboxy groupsor one to four 1H-1,2,4-triazol-3-ylthio groups, respectively, toincorporate the photopolymerizable groups as described above.Alternatively, the photopolymerizable groups may be incorporated intothe diazotiazable amine and/or coupler portion prior to the synthesis ofthe azo dyes of Formula XIII and XIV.

Typical aromatic amine coupling components (HZ) which containphotopolymerizable groups and are useful in preparing colorants ofFormula XIII have the following structures:

Typical aromatic amine coupling components (HZ₁) which containcopolymerizable groups and are useful in preparing colorants of FormulaXIV have the following structures:

In the structures for coupling components HZ and HZ₁ above, R₁₅, R₁₆,R₁₈, R₁₉, R₂₀, R₂₄, X and Y have the meaning previously ascribed tothem.

Colorants of Formula XV, XVII and XVIII which correspond to colorantscontaining the methine, 3-aryl-2,5-dioxypyrroline and3-aryl-5-dicyanomethylene-2-oxypyrroline chromophores, respectively, maybe prepared by reacting the intermediate aromatic moiety R₂₅H, asdefined previously, which contains one or more photopolymerizable groupswith either (a) Vilsmeier complex (e.g., from POCl₃/DMF), followed byreaction with the active methylene compound,

to produce colorants of Formula XV, XVII, and XVIII, respectively,wherein R₁₆′ is hydrogen. Compounds of Formula XVII and XVIII, whereinR₁₆ is hydrogen, can be further reacted to introduce photopolymerizablegroups if desired.

A third alternative preparative method for azo colorants having FormulaXIII and XIV involves the reaction of electron rich coupler precursorscontaining at least one —CO₂H or 1(H)-1,2,4-triazolyl-3-ylthio group,respectively, with hydroxyalkylating agents to introduce —CO₂—R₁—OH and

groups. These couplers then are reacted with the desired diazonium saltsto produce azo dye containing the hydroxy groups which are then reactedfurther to introduce the photopolymerizable Q groups into the finalcolorant. Similarly, this method may be employed in the preparation ofthe colorants having Formulae XV, XVI and XVII by reacting the acidiccolored intermediates containing the methine, 3-aryl-2,5-dioxypyrrolineor 3-aryl-5-dicyano methylene-2-oxypyrroline chromophores, respectively,to introduce the photopolymerizable group after the chromophore isformed.

As is known to those skilled in the art, the 1 (H)-1,2,4-triazolylmoiety of Formula II is a mixture of isomers having the structures:

but that the isomer shown in Formula II probably predominates.

COLORANT EXAMPLES

The copolymerizable dye compounds provided by the present invention andthe preparation thereof are further illustrated by the followingexamples.

Example 1

A mixture of 1,5-bis-(2-carboxyphenylthio) anthraquinone (U.S. Pat. No.4,359,570, Example 1) (5.13 g, 0.01 mol), potassium carbonate (2.84 g,0.02 mol) and N, N-dimethylformamide (DMF, 100 mL) was stirred andheated to about 100° C. To the stirred mixture, was added 4-vinylbenzylchloride (Aldrich, 3.76 g, 0.022m). Thin-layer chromatography (TLC)using a 50/50 mixture of tetrahydrofuran(THF)/cyclohexane after heatingthe reaction mixture at about 105° C. for 30 min. showed only one spotwith no starting material or mono-reacted product being observed. Thereaction mixture was heated for an additional 20 minutes and the yellowdye precipitated by the addition of a mixture of methanol and water. Thesolid dye was collected by filtration, washed with water and then with alittle methanol. The yield of air-dried product was 6.85 g (92% of thetheoretical yield). Field desorption mass spectrometry (FDMS) supportedthe following structure:

An absorption maximum at 447 nm was observed in the UV-visibleabsorption spectrum in DMF.

Example 2

A mixture of 1,5-bis-(2-carboxyanilino) anthraquinone (U.S. Pat. No.4,359,570, Example 2) (4.78 g, 0.01 mol), potassium carbonate (2.76 g,0.02 mol) and DMF (100 mL) was stirred and heated to about 90° C. and4-vinylbenzyl chloride (Aldrich, 3.76 g, 0.022 mol) was added andheating and stirring continued at about 100° C. for 60 min. TLC (50/50THF/cyclohexane) showed complete reaction. Methanol (120 mL) was addedgradually with stirring to precipitate the red product, which wascollected by filtration, washed with water and then dried in air(yield—6.18 g, 87% of the theoretical yield). FDMS supports thefollowing structure:

Example 3

A mixture of 1,5-bis-(isobutylamino)-4,8-bis-(2-carboxyphenylthio)anthraquinone (U.S. Pat. No. 6,197,223, Example 2) (6.54 g, 0.01 mol),potassium carbonate (2.76 g, 0.02 m) and DMF (150 mL) was stirred andheated to about 100° C. To the stirred reaction mixture was added4-vinylbenzyl chloride (3.76 g, 0.02 mol). The reaction mixture washeated at 95-100° C. for about 60 minutes The reaction mixture wascooled and the gummy product was drowned out by the addition ofmethanol/water. The liquid was decanted off and the product trituratedwith methanol. The resulting dark blue solid was collected byfiltration, washed with methanol and dried in air (yield—6.95 g, 78% ofthe theoretical yield). FDMS supported the following structure:

Absorption maxima at 600 nm and 645 nm were observed in the UV-visibleabsorption spectra in DMF.

Example 4

A mixture of1,5-bis-(2-carboxyphenylthio)-4,8-bis-(4-tolylthio)-anthraquinone (U.S.Pat. No. 6,197,223) (7.56 g, 0.01 mol), potassium carbonate (K₂CO₃) andDMF (300 mL) was stirred and heated to about 100° C. and then4-vinylbenzyl chloride (3.84 g, 0.025 mol) was added. The reactionmixture was heated- and stirred at about 100° C. for 60 minutes. TLC(50/50 THF/cyclohexanol) showed complete reaction. After cooling, thesticky product was obtained by drowning the reaction mixture withmethanol/water. The red product solidified upon standing in contact withmethanol and was collected by filtration and dried in air (yield—7.67 g,78% of the theoretical yield). FDMS supported the following structure:

An absorption maximum was observed at 520 nm in the UV-visibleabsorption in DMF.

Example 5

A mixture of 1,5-bis-[(1H)-1,2,4-triazol-3ylthio)] anthraquinone (U.S.Pat. No. 3,689,501) (4.06 g, 0.01 mol), potassium carbonate (2.76 g,0.02 mol) and DMF (100 mL) was stirred and heated to about 100° C. and4-vinylbenzyl chloride (3.76 g, 0.022 mol) was added. TLC (50/50THF/cyclohexane) still showed some mono-substituted product afterheating the reaction mixture for 2 hrs. Additional quantities of4-vinylbenzyl chloride (4.14 g) and potassium chloride (1.38 g) wereadded and heating continued for another hour to complete the reaction. Agummy yellow solid was produced by drowning the cooled reaction mixturewith water. The product was washed by decantation with water and thendissolved in DMF. The DMF solution was drowned gradually into cold waterwith good stirring and the yellow solid was collected by filtration anddried in air (3.46 g, 54% of the theoretical yield). FDMS supported thefollowing structure:

An absorption maximum at 420 nm was observed in the UV-visibleabsorption spectrum in DMF.

Example 6a

A mixture of 1,5-bis-(2-carboxyphenylthio) anthraquinone (U.S. Pat. No.4,359,570, Example 1) (30.6 g, 0.06 mol), ethylene carbonate (88.09, 1.0mol), ethylene glycol (50 mL) and pulverized potassium iodide (5.2 g)was heated and stirred at about 125° C. for about 2.0 hours and thenallowed to cool. The reaction mixture was drowned into cold water (150mL) with stirring. The yellow solid was collected by filtration, washedwith warm water and dried in air (yield-35.2 g, 97.8% of the theoreticalyield). FDMS supported the following structure:

Example 6b

A mixture of the product of Example 6a (6.0 g, 0.01 mol), DMF (25 mL)and 3-isopropenyl-∝,∝-dimethylbenzyl isocyanate (6 mL, 0.03 mol) washeated and stirred, under nitrogen at about 95-100° C. for about 48hours. Triethylamine (0.5 mL) was added and heating continued for anadditional 48 hours. Water (60 mL) was added portionwise to the hotreaction mixture with stirring. After allowing to cool to roomtemperature, the yellow product was collected to filtration, washed withwater and dried in air. Essentially a quantitative yield of thefollowing product was obtained:

Example 7

The dye of Example 6a above (2.0 g, 3.33 mmol) and toluene (20 mL) weremixed and stirred while most of the toluene was removed under reducedpressure. DMF (50 mL), 4-(dimethylamino)pyridine (DMAP, 82 mg),triethylamine (1.4 mL), hydroquinone (50 mg) and methacrylic anhydride(1.53 g, 9.99 mmol) were added and the reaction mixture stirred at roomtemperature for 15 hours. The yellow functionalized dye which wasprecipitated by drowning into water (200 mL) and allowing to stand forseveral days was collected by filtration, washed with water and 1:1methanol: water and dried in vacuo. The yield was 2.23 g (91% of thetheoretical yield). FDMS supported the following structure:

An absorption maximum at 444 nm was observed in the UV-visibleabsorption spectrum in DMF.

Example 8a

A mixture of 1,5-bis-(carboxyanilino) anthraquinone (U.S. Pat. No.4,359,570, Example 2) (59.75 g, 0.125 mol), ethylene carbonate (165 g,1.875 mol), ethylene glycol (550 mL) and pulverized potassium iodide(11.3 g) was heated at 120-125° C. for 6.5 hours and the mixture allowedto cool. Methanol (400 mL) was added to the stirred reaction mixture.The red solid was collected by filtration, washed with water and driedin air (yield—69.5 g, 98.2% of the theoretical yield). FDMS supportedthe following structure:

Example 8b

A portion (2.0 g, 3.53 mmol) of the dye of Example 8a above was mixedwith toluene (10 mL) and most of the toluene removed under vacuum. DMF(50 mL), DMAP (86 mg), triethylamine (1.5 mL), hydroquinone (20 mg) andmethacrylic anhydride (1.63 g, 10.6 mmol) were added and the resultingsolution was stirred for 15 hours at room temperature. The reactionmixture was drowned into water (200) and allowed to stand at roomtemperature for several days. The functionalized red dye was collectedby filtration, washed with water and dried in vacuo (yield—2.10 g. 85%of the theoretical yield). FDMS supported the following structure:

An absorption maximum at 525 nm was observed in DMF solution in theUV-visible absorption spectrum.

Example 9

A portion (2.0 g, 3.53 mmol) of the dye from Example 8a above was mixedwith toluene and stirred while most of the toluene was removed underreduced pressure. DMF (50 mL), DMAP (86 mg), triethylamine (1.5 mL),hydroquinone (20 mg) and crotonic anhydride (1.63 g, 10.6 mmol) wereadded and the reaction mixture was stirred for 24 hours. Thefunctionalized red dye was isolated by drowning into water (200 mL),allowing the mixture to stand for a little while and then collecting byfiltration. After washing with water the dye was dried in vacuo(yield—2.119, 85% of the theoretical yield). FDMS supported thefollowing structure:

An absorption maximum at 522 nm in DMF solution was observed in theUV-visible light absorption spectrum.

Example 10

A mixture of a portion (2.0 g, 3.33 mmol) of the dye of Example 6a aboveand toluene (10 mL) was stirred and most of the toluene removed undervacuum. DMF (50 mL), DMAP (86 mg) triethylamine (1.4 mL), hydroquinone(20 mg) and crotonic anhydride (7.54 g, 9.99 mmol) were added. Thereaction mixture was stirred at room temperature for 24 hours anddrowned into water (200 mL) with stirring. The mixture was allowed tostand awhile and the functionalized yellow dye was collected byfiltration, washed with water and dried in vacuo (yield 2.019, 82% ofthe theoretical yield). FDMS supported the following structure:

An absorption maximum at 446 nm was observed in DMF in the UV-visiblelight absorption spectrum.

Example 11a

A mixture of 1-chloroanthraquinone (97.2 g, 0.40 mol), thiosalicylicacid (61.6 g, 0.40 mol), potassium acetate (80 g, 0.80 mol), cuprouschloride (0.5 g) and 2-ethoxyethanol (500 ml) was stirred and heated atreflux (130-135° C.) for 6.5 hours. After allowing to cool, the reactionproduct was collected by filtration and washing with methanol. The stillmoist cake was slurried in water (750 ml) and the mixture acidified bythe addition of concentrated hydrochloric acid (75 ml). The mixture wasstirred at ambient temperature for thirty minutes and the yellow productwas collected by filtration, washed with water, washed with a littlemethanol and dried in air (yield—110.6 g, 76.87% of the theoreticalyield). Field desorption mass spectrometry (FDMS) supported thefollowing structure:

Example 11b

A mixture of 1-(2-carboxyphenylthio) arthraquinone (Example 11 a) (3.60g, 0.01 mol), potassium carbonate (1.38 g, 0.01 mol) andN,N-dimethylformamide (DMF), (70 ml) was heated and stirred. At 70° C.,4-vinylbenzyl chloride (1.87 g, 0.011 mol) was added and the reactionmixture was heated to about 100° C. After being heated at about 100° C.for forty minutres, the reaction mixture was allowed to cool and thenwas drowned with stirring into water (200 ml). After standing overnightat room temperature the yellow solid was collected by filtration, washedwith water and dried in air. The yield of product was 4.40 g, 92% of thetheoretical yield. FDMS analysis supported the following structure:

An absorption maximum at 425 nm was observed in the UV-visible lightabsorption spectrum in DMF.

Example 12a

A mixture of thiosalicylic acid (4.63 g, 0.03 mol), potassium carbonate(8.70 g, 0.06 mol) and DMF (75 ml) was heated and stirred at 100° C. fortwo hours. This mixture was allowed to cool to room temperature andadded to a stirred mixture of 1,5-dichloro-4,8-dinitroanthraquinone(5.51 g, 0.015 mol) and DMF (150 ml) which had been cooled to about 0°C. A slight exotherm of 2-3° C. was observed. The mixture was stirred atabout 0-5° C. for thirty minutes and then allowed to stand overnight atroom temperature. A second mixture of thiosalicylic acid (4.63 g, 0.03mol), potassium carbonate (8.73 g, 0.06 mol) and DM,F (40 ml), which hadbeen stirred for 1.5 hours at room temperature, was added to thepreviously described mixture. After being heated and stirred at about100° C. for five hours, the reaction mixture was cooled to roomtemperature and drowned into water (600 ml) with stirring. After themixture was acidified by the addition of glacial acetic acid, the darkred product was collected by filtration, washed with water and airdried. (yield—10.70 g, 87.3% of the theorectical yield). FDMS supportedthe following structure:

Example 12b

A mixture of 1,4,5,8-tetra(2-carboxyphenylthio) anthraquinone (1.22 g,1.5 mmol) (Example 12a), potassium carbonate (0.83 g, 6.0 mmol) and DMF(20 ml) was stirred and 4-vinylbenzyl chloride (1.01 g, 6.6 mmol) wasadded. The reaction mixture was heated at about 100° C. for thirtyminutes. After cooling to room temperature, the mixture was drowned intomethanol. The dark red solid was collected by filtration, washed withmethanol and dried in air. The yield of product was 1.58 g, 82% of thetheoretical yield. FDMS supported the following structure:

An absorption maximum at 543 nm was observed in the UV-visible lightabsorption spectrum in DMF solvent.

Example 13a

A mixture of brominated diaminoanthrarufin (3.49 g, 0.01 mol),thiosalicylic acid (3.08 g, 0.02 mol), potassium carbonate (5.53 g, 0.04mol), cuprous chloride (0.30 g) and DMF (50 ml) was heated at 95-100° C.for about six hours. The reaction mixture was cooled and then drownedinto acetone (400 ml). The solid potassium salt of the product wascollected by filtration and then redissolved in hot water (300 ml). Thefree acid was obtained by acidification with glacial acetic acid,collecting by filtration, washing with water and drying in air (yield3.40 g). FDMS showed the product to be a mixture of mono-andbis-(2-carboxyphenylthio) substituted diamino-anthrarufin having thefollowing structure:

Example 13b

A mixture of a portion of the product from Example 13a (0.85 g),potassium carbonate (0.34 g) and DMF (20 ml) was stirred and heated toabout 100° C. and 4-vinylbenzyl chloride (0.38 g) was added. Thereaction mixture was stirred at about 100° C. for about thirty minutes,cooled to room temperature and then drowned into methanol (200 ml). Thedark blue product was collected by filtration, washed with methanol,water and then again with methanol to promote drying. The air-driedproduct weighed (0.69 g). FDMS showed the product to have the followingstructure:

wherein the monosubstitued product was the major predominate structurepresent. An absorption maximum at 641 nm was observed in the UV-visiblelight absorption spectrum.

Example 14a

A mixture of 1,8-diamino-2,7-dibromo-4,5-dihydroxyanthraquinone (2.14 g,0.005 mol), thiosalicylic acid (1.69 g, 0.011 mol), potassium carbonate(3.0 g), cuprous chloride (0.30 g) and DMF (45.0 ml) was heated at steambath temperature for about 6.0 hours. The reaction mixture was cooledand drowned into acetone (500 ml). The resulting solid was collected byfiltration and the acetone-wet material was dissolved in warm water.Acetic acid was added to precipitate the diacid product which wascollected by filtration, washed with water and dried in air (yield—2.60g).

Example 14b

A mixture of 1,8-diamino-4,5-dihydroxy-2,7-bis(carboxyphenylthio)anthraquinone (1.15 g, 2.0 mmol), (from Example 14a) potassium carbonate(0.56 g, 4.0 mmol) and DMF (20 ml) was heated to about 100° C. and4-vinylbenzyl chloride (0.68 g, 4.4 mml) was added. Stirring and heatingwere continued at about 100° C. for four hours. The product was isloatedby drowning into water and collecting the product by filtration. Theproduct comprises primarily the compound having the following expectedstructure:

When the product was dissolved in DMF a bright cyan color was obtained.

Example 15

A mixture of1-cyano-6(3′,5′-dicarboxyphenylamino)-3-methyl-3H-dibenz[f,lj]isoquinoline-2,7-dione(Example 119a of U.S. Pat. No. 6,197,223) (4.65 g, 0.01 mol), potassiumcarbonate (0.02 mol) and DMF (100 ml) was stirred and heated in about90° C. and 4-vinylbenzyl chloride (3.73 g 0.022 mol) was added. Afterbeing heated at about 110° C. for 3.0 hours, thin-layer chromatography(90/10 THF/cyclohexane) showed the reaction to be complete and thereaction mixture was cooled to room temperature. Methanol (100 ml) wasadded with stirring to the reaction mixture. After being allowed tostand overnight at room temperature, the product was collected byfiltration, washed with methanol and dried in air (yield—3.80 g, 54% ofthe theoretical yield) and has the structure:

A bright violet color was obtained when the product was dissolved inDMF.

Example 16a

A mixture of 6-bromo-1-cyano-3H-dibenz[f,ij]isoquinoline-2,7-dione (3.65g, 0.01 mol) thiosalicylic acid (1.54 g, 0.01 mol), potassium carbonate(2.76 g, 0.02 mol) and DMF (60 ml) was stirred and heated at about95-100° C. for 1.5 hours. After allowing to cool, the reaction mixturewas drowned into water (100 ml) and the mixture acidified by theaddition of glacial acetic acid. The red solid was collected byfiltration, washed with water and dried in air. The yield of product was4.38 g (100% of the theoretical yield). FDMS supported the followingexpected structure:

Example 16b

The carboxy anthrapyridone dye of Example 16a(4.38 g, 0.01 mol),potassium carbonate (1.38 g, 0.01 mol) and DMF (100 ml) were stirredtogether and heated to about 100° C. for 30 minutes. After cooling,water (100 ml) was added dropwise to the stirred reaction mixture. Theprecipitated red product was collected by filtration, washed with waterand dried in air (yield—4.92 g, 89% of the theoretical yield). FDMSsupported the following structure:

An absorption maximum was observed at 523 nm in the UV-visible lightabsorption spectrum in DMF as solvent.

Example 17

A mixture of 2,5-dianilinoterephthalic acid (3.48 g, 0.01 mol),potassium carbonate (2.76 g) and DMF (100 ml) was stirred and heated to100° C. and 4-vinylbenzyl chloride (3.76 g, 0.11 mol) was added. Heatingwas continued for 1.0 hour and then the cooled reacting mixture wastreated with 200 ml of water which was added dropwise. The orangeproduct was collected by filtration, washed with water and dried in air(yield-5.58 g, 96% of the theoretical yield). FDMS supported thefollowing expected structure:

An absorption maximum was observed at 471 nm in the UV-visible lightabsorption spectrum in DMF as solvent.

Example 18a

A mixture of 1,5-bis-[(1H)-1,2,4-triazolythio]anthraquinone (8.12 g,0.02 mol), ethylene carbonate (29.4 g, 0.33 mol), ethylene glycol (30ml) and pulverized potassium iodide (2.0 g) was heated and stirred at125° C. for 3.5 hours. The reaction mixture was allowed to cool andwater (100 ml) was added dropwise with stirring. The yellow product(1,5-bis-[[1 (2-hydroxy-ethyl)-1,2,4-triazolyl-3-yl]thio]anthraquinone)was collected by filtration, washed with water and dried in air (yield 06.8 g, 69% of the theoretical yield).

Example 18b

A mixture of a portion (1.0 g, 0.0020 mol) of the product from Example18a, DMF (25 ml), hydroquinone (10 mg), 4-(dimethylamino)-pyridine (49mg) and methacrylic anhydride (0.91 ml) was stirred at room temperatureand triethylamine (0.85 ml) was added dropwise. The reaction mixture wasstirred at room temperature for 24 hours and then drowned into water.The yellow product was collected by filtration, washed with water anddried in air (yield—0.85 g, 67% of the theoretical yield). FDMSsupported the following expected structure:

An absorption maximum at 422 nm was observed UV-visible spectrum in DMFas solvent.

Example 19a

A mixture of 1,5-bis-(cyclohexylamino)-4,8-bis-(2′-carboxyphenylthio)anthraquinone (49.5 g, 0.07 mol), ethylene carbonate (149 g, 1.69 mol),pulverized potassium iodide (42 g) and ethylene glycol (300 ml) washeated and stirred to 100° C. and held at about 110° C. for about 1.0hour (some foaming resulted). Heating and stirring were continued at125° C. for about 2.5 hours and the cooled reaction mixture was thendrowned into 2500 ml of methanol. Some water was added to the methanolsolution so further precipitate the blue solid, which was collected byfiltration, washed with water and dried in air (yield-36.3 g, 62% of thetheoretical yield). FDMS showed that the structure was that of thestarting material for Example 19b.

Example 19b

A mixture of a portion of the1,5-bis(cyclohexylamino)-4,8-bis-[2′-hydroxyethoxycarbonyl)-phenylthio]anthraquinone from Example 19a (1.0 g, 0.00126 mol), DMF (25 ml),hydroquinone (10 mg), DMAP (30.8 mg) and methacrylic anhydride (0.563ml) was stirred and triethylamine (0.527 ml) was added dropwise. Thereaction mixture was stirred for 24 hours at room temperature and thendrowned into water (50 ml). The blue product was collected byfiltration, washed with water and dried in air (yield—0.65 g, 56% of thetheoretical yield). FDMS supported the following expected structure:

Absorption maxima at 603 nm and 646 nm were observed in the UV-visibleabsorption spectrum in DMF solution.

Example 20a Preparation of Azo Dye Coupler

A mixture of 3-acetamido-N,N-bis-(4-carboxybenzyl)aniline (12.5, 0.03mol) (prepared as described in Example 91b of U.S. Pat. No. 6,197,223),ethylene carbonate 44 g, 0.50 mol), ethylene glycol (60 ml) andpulverized potassium iodide (2.68 g) was stirred and heated at 120-125°C. for 4.0 hours. Water (150 ml) was added drop wise with stirring tothe cooled reaction mixture. The resulting solid was collected byfiltration, washed with water and dried in air (yield—12.9 g, 85% of thetheoretical yield). FDMS supported the following structure:

EXAMPLE 20b Preparation of Intermediate Azo Dye

A mixture of 5-amino-4-cyano-3-methylisothiazole (1.39 g, 0.01 mol) andwater (17.5 ml) was stirred and cooled in an ice bath. Concentratedsulfuric acid (8.3 ml) was added portionwise below about 40° C. Nitrosylsulfuric acid (40%) (3.2 g, 0.01 mol) was then added with stirring belowabout 3° C. The orange solution was stirred at −2° C. to +2° C. for 2.0hours and then added to a chilled solution of a portion (5.0 g, 0.01mol) of the coupler from Example 20a dissolved in water (100 ml)containing concentrated sulfuric acid (10 ml) and 1:5 acid (1 partpropionic acid: 5 parts acetic acid by weight) (50 ml). The couplingmixture was kept cold and the mineral acid neutralized by the additionof ammonium acetate with stirring. After being allowed to stand forabout 1.0 hour with occasional stirring, the coupling mixture wasdrowned by the addition of water. The solid dye was collected byfiltration, washed with water and dried in air. After being reslurriedin hot methanol and allowing to cool, the dye was collected byfiltration, washed with methanol, and dried in air (yield—3.9 g, 59% ofthe theoretical yield). FDMS supported the following structure:

An absorption maximum was observed at 543 nm in the UV-Visible lightabsorption spectrum in DMF solution.

Example 20c

A portion of the azo dye from Example 20b (0.50 g), DMF (25 ml),hydroquinone (5 mg) DMAP (19 mg) and methacrylic anhydride (0.34 ml)were mixed and stirred and triethylamine (0.32 ml) was added drop wise.After being stirred at room temperature for 24 hours, the reactionmixture was drowned into water, collected by filtration, washed withwater and dried in air (yield—0.5 g). FDMS supported the followingexpected structure:

An absorption maximum was observed at 543 nm in the UV-visibleabsorption spectrum in DMF solution.

Example 21a

To p-dioxane (600 ml) was added N-(α-cyanoacetyl)piperidine (30.4 g,0.20 mol) and the solution was stirred and cooled to about 5° C., atwhich temperature phosphorous oxychloride (30.6 g, 0.2 mol) was addeddrop-wise while keeping the temperature below 5° C. While stirring thereaction mixture at about 30° C., 1-amino-4-bromoanthraquinone (58.6 g,0.194 mol) was added portion-wise. The reaction mixture was then heatedat about 95° C. for 12 hours and then drowned into ice/water mixture. A20% aqueous solution of sodium carbonate was added gradually until a pHof about 9 was obtained. The red product was collected by filtrationwashed with water are dried in air (66.3 g, 82% of the theoreticalyield).

Example 21b

A portion (20.0 g, 0.050 mol) of the6-bromo-1-cyano-2-piperidino-7H-dibenz[f,ij]-isoquinoline-7-one whichwas prepared in Example 21a, ethylene glycol (500 ml), dimethyl5-aminoisophthalate (20.0 g, 0.1 mol), potassium acetate (10.0 g) andcupric acetate (10.0 g) were mixed and stirred and heated gradually toabout 180° C. and held for 1.5 hours, whereupon the reaction mixture wascooled and drowned into water (800 ml). The product was collected byfiltration, washed with water and dried in air (yield—46.0 g). FDMSindicated that the product consisted largely of the following structure:

Example 21c

A mixture of a portion (2.0 g, 0.0033 mol) of the product of Example21b, DMF (25 ml), hydroquinone (20 mg), DMAP (80.6 mg) and methacrylicanhydride (1.47 ml) were mixed and stirred while triethylamine (1.4 ml)was added drop-wise. Stirring was continued at room temperature for 24hours. The reaction mixture then was poured into methanol (50 ml) andthen water (100 ml) was added to precipitate the product, which wascollected by filtration, washed with water and dried in air (yield—2.2g, 90% of the theoretical yield). FDMS indicated that the productconsisted primarily of the compound having the expected structure:

The product had a magenta color when dissolved in DMF.

Example 22a

To 40% nitrosylsulfuric acid (9.6 g, 0.03 mol-100% basis) was added 1:5acid (15 ml) with stirring at below 25° C. While cooling further,2-chloro-4-nitroaniline (5.18 g, 0.03 mol) was added portion wise belowabout 8° C. Stirring was continued at about 3-8° C. for 2 hours. Thediazotization reaction mixture was filtered through a fritted glassfunnel to remove a few coarse particles of undissolved2-chloro-4-nitroaniline. The diazonium salt solution was added to achilled solution of 3-acetamido-N,N-bis-(4-carboxy-behzyl) aniline (12.6g, 0.03 mol) dissolved in 1:5 acid (120 ml) at below about 10° C. withstirring. The coupling mixture was neutralized by the portion-wiseaddition of ammonium acetate until neutral to Congo Red test paper andthen stirred for about 1.0 hour at below 15° C. Cold water (500 ml) wasadded to the mixture. The solid red product was collected by filtration,washed with water and dried in air. After reslurrying in hot methanol,cooling, collecting by filtration, washing with methanol and drying inair 10.1 g (56% of the theoretical yield) of the product was obtainedwhich had the following structure:

Example 22b

A mixture of a portion (0.60 g, 0.001 mol) of the bis-carboxy azocompound from Example 22a, potassium carbonate (0.28 g), DMF (20 ml) and4-vinylbenzyl chloride (0.35 mol, 0.0022 mol) was stirred at about 100°C. for 2.5 hours. After cooling the reaction mixture was diluted withmethanol to precipitate the product which was collected by filtration,washed with methanol and then slurried in water to remove any salts.After being collected by filtration, washed with water and dried in air,0.35 g (42% of the theoretical yield) of product was obtained. FDMSsupported mostly the following structure:

Example 23a

Thiosalicylic acid (46.3 g, 0.30 mol) was mixed with DMF (400 ml) andstirred. Potassium carbonate (82.8 g, 0.60 mol) was added and thereaction mixture was gradually heated to about 95-100° C., held for 1.5hours. After being allowed to cool, the mixture was added portion wiseto a stirred mixture of 1,5-dichloro-4,8-dinitroanthraquinone (54.9 g,0.150 mol) and DMF (1.0 L). The reaction mixture was stirred at about 15minutes at 10-15° C. Cooling was removed and stirring was continued atambient temperature for 3 hours. A solution of 4-thiocresol (37.3 g, 0.3mol) in DMF (250 ml) was added and then the whole reaction mixture washeated at about 95° C. for about 8 hours. After allowing to cool, thereaction mixture was drowned into a mixture of concentrated HCl (100 ml)water (1900 ml) and some crushed ice. The product was collected byfiltration washed with water and dried in air (yield 109.8 g).

Example 23b

A mixture of1,5-bis(2-carboxyphenylthio)-4,8-bis-(4-tolythio)-anthraquinone producedas described in Example 23a (3.78 g, 0.005 mol), ethylene carbonate(5.28 g, 0.06 mol), ethylene glycol (25 ml) and pulverized potassiumiodide (1.5 g) was heated and stirred at about 125° C. for 4.0 hours.After being allowed to cool, the product was precipitated by theaddition of methanol. The solid was collected by filtration, washed withmethanol, and dried in air (yield—2.94 g, 70% of the theoretical yield).FDMS showed that the product consisted primarily of a compound havingthe structure:

Example 23c

A portion (0.5 g, 0.00059 mol) of the product from Example 23b, DMF (10ml), DMAP (14.4 mg), hydroquinone (5 mg) and methacrylic anhydride(0.265 ml) were mixed and stirred at room temperature whiletriethylamine (0.248 ml) was added dropwise. Stirring was continued atroom temperature for 24 hours. Methanol (50 ml) was added to thereaction mixture and then the product was precipitated by the additionof water (75 ml). The solid was collected by filtration, washed withwater, and dried in air (yield—0.47 g, 81% of the theoretical yield).FDMS supported the following structure:

The product produced a bright red color when dissolved in DMF.

Example 24a

A mixture of 2,5-dianilinoterephthalic acid (20.90 g, 0.06 ml), ethylenecarbonate (63.40 g, 0.72 mol), ethylene glycol (65 ml) and pulverizedpotassium iodide (17.5 g) was stirred and heated under nitrogen to about120° C. Considerable foaming occurred at about 120° C. but soon subsidedand the temperature was increased to about 125° C. and stirringcontinued for 3.5 hours. The reaction mixture was cooled and methanol(100 ml) was added to the reaction mixture dropwise. The orange solidwhich crystallized was collected by filtration, washed with water anddried in water (yield—14.4 g, 55% of the theoretical yield). FDMS showedthat the product was the bis-(2-hydroxyethyl) ester having the formula:

Example 24b

The orange diol colorant as prepared in Example 24a (50.0 g, 0.115 mol),acetone (150 ml), DMAP (2 g), t-butylhydroquinone (1 g) andtriethyl-amine (50 g) were mixed together and the mixture was stirredand heated to 40° C. and methacrylic anhydride (50 g) was addeddropwise. A slight exotherm was observed and heating was continued for1.0 hours. The reaction solution was allowed to cool and water (150 ml)was added drop wise over about 30 minutes to precipitate the productwhich was collected by filtration, washed with water and dried at about60-70° C. under vacuum. The yield of bright orange solid was 45.0 g, 66%of the theoretical yield.FDMS supported the following structure:

Additional examples of the colorant compounds which contain one or moreethylenically-unsaturated (vinyl), photopolymerizable radicals accordingto the present invention are set forth in the examples of Tables 1-XIV.These compounds may be prepared by procedures analogous to thosedescribed in the preceding examples and/or by published techniques.TABLE I Azo Colorants of Formula XIII

Example No. D R₁₅ R₁₆ R₁₇ 25 4-NO₂-phenyl H —CH₂—C₆H₄-4-CO₂—CH₂CH₂——CH₂—C₆H₄-4-CO₂—CH₂CH₂— OCOC(CH₃)═CH₂ OCOC(CH₃)═CH₂ 26 2—Cl-4-NO₂- 3CH₃—CH₂—C₆H₄-4-CO₂—CH₂CH₂— —CH₂—C₆H₄-4-CO₂—CH₂CH₂— phenyl OCOC(CH₃)═CH₂OCOC(CH₃)═CH₂ 27 2—Br-4-CN-phenyl 3-NHCOCH₃ —CH₂—C₆H₄-4-CO₂—CH₂CH₂——CH₂—C₆H₄-4-CO₂—CH₂CH₂— OCOC(CH₃)═CH₂ OCOC(CH₃)═CH₂ 28 2,6-di-CN-4-NO₂-3-NHCOCH₃ —CH₂—C₆H₄-4-CO₂—CH₂CH₂— —CH₂—C₆H₄-4-CO₂—CH₂CH₂— phenylOCOC(CH₃)═CH₂ OCOC(CH₃)═CH₂ 29 2-Br-4,6-di-NO₂- 2-OCH₃-5-—CH₂—C₆H₄-4-CO₂—CH₂CH₂— —CH₂—C₆H₄-4-CO₂—CH₂CH₂— phenyl NHCOCH₃OCOC(CH₃)═CH₂ OCOC(CH₃)CH₂ 30 2-Cl-4-CH₃SO₂- 3-NHCOCH₃ —C₂H₅—CH₂—C₆H₄-4-CO₂—CH₂CH₂— phenyl OCOC(CH₃)═CH₂ 31 2-CN-4-CH₃SO₂ 3-NHCOCH₃—C₂H₅ —CH₂—C₆H₄-4-CO₂—CH₂CH₂— phenyl OCOC(CH₃)═CH₂ 32 2-CN-4-CH₃SO₂—3-CH₃ —C₂H₅ —CH₂CH₂O—C₆H₃-3,5-bis- phenyl (—CO₂CH₂—C₆H₄-4-CH═CH₂) 332-Br-4-NO₂- 3-NHCOCH₃ —CH₂—C₆H₄-4-(CO₂—CH₂— —CH₂—C₆H₄-4-(CO₂—CH₂— phenylC₆H₄-4-CH═CH₂) C₆H₄-4-CH═CH₂) 34 5-C₂H₅S-1,3,4- 3-NHCOCH₃—CH₂—C₆H₄-4-(CO₂CH₂— —CH₂—C₆H₄-4-(CO₂—CH_(2—) thiadiazol-2-ylC₆H₄-4-CH═CH₂) C₆H₄-4-CH═CH₂) 35 6—CH₃SO₂- 3-NHCOCH₃—CH₂—C₆H₄-4-(CO₂—CH₂— —CH₂—C₆H₄-4-(CO₂—CH₂— benzothiazol-2-ylC₆H₄-4-CH═CH₂) C₆H₄-4-CH═CH₂) 36 5,6-di-Cl- 3-NHCOCH₃—CH₂—C₆H₄-4-—(CO₂—CH₂— —CH₂—C₆H₄-4-(CO₂—CH₂— benzothiazol-2-ylC₆H₄-4-CH═CH₂) C₆H₄-4-CH═CH₂) 37 5-NO₂- 3-NHCOCH₃ —CH₂—C₆H₄-4-(CO₂—CH₂——CH₂—C₆H₄-4-(CO₂—CH₂— benzothiazol-2-yl C₆H₄-4-CH═CH₂) C₆H₄-4-CH═CH₂) 384-Br-3-CH₃-iso- 3-NHCOCH₃ —CH₂—C₆H₄-4-—(CO₂—CH₂— —CH₂—C₆H₄-4-(CO₂—CH₂—thiazol-5-yl C₆H₄-4-CH═CH₂) C₆H₄-4-CH═CH₂) 39 3-CH₃-4-CN-iso- 3-NHCOCH₃—CH₂—C₆H₄-4-(CO₂—CH₂— —CH₂—C₆H₄-4-(CO₂—CH₂— thiazol-5-yl C₆H₄-4-CH═CH₂)C₆H₄-4-CH═CH₂) 40 3-SCH₃-1,2,4- H —CH₂CH₂—CO₂—CH₂CH₂——CH₂CH₂—CO₂—CH₂CH₂— thiadiazol-5-yl OCO(CH3)═CH2 OCO(CH3)═CH2 415-NO₂-thiazol-2-yl 3-CH₃ —CH₂CH₂O—C₆H₄-2-(CO₂— —C₂H₅ CH₂—C₆H₄-4-CH═CH₂)42 2-CH₃CO-4-NO₂- 3-NHCOCH₃ —CH₂CH₂S—C₆H₄-2-(CO₂— —C₂H₅ thien-5-ylCH₂CH₂—C₆H₄-4-CH═CH₂) 43 4-CH₃CO-2-NO₂- 3-CH₃ —CH₂CH₂S—C₆H₄-2-(CO₂——CH₂CH₂S—C₆H₄-2-(CO₂— thien-5-yl CH₂—C₆H₄—-4-CH═CH₂) CH₂—C₆H₄-4-CH═CH₂)44 2,4-di-CH₃O₂C-4- H —CH₂CH₂O—C₆H₄-4-(CO₂— —C₂H₅ CH₃-thien-5-ylCH₂CH₂OCO—CH═CH₂) 45 5-NO₂-benziso- 3-NHCOC₂H₅ —CH₂—C₆H₄-4-(CO₂— —C₂H₅thiazol-3-yl CH₂CH₂CH₂OCO—CH═CH₂) 46 4-phthalimidyl 3-NHCOCH₃—CH₂CH₂SO₂—C₆H₄-2-(CO₂— —C₂H₅ CH₂—CH(CH₃)—OCO— CH═CH₂) 47 4-Br—N—C₂H₅-5-phthalimidyl 3-CH₃

—C₂H₅

TABLE II Methine Colorants of Formula XV

Example No. AM R₁₅ R₁₆ R₁₇ 48 ═C(CN)CN H —C₂H₅ —CH₂—C₆H₄-4-(CO₂—CH₂CH₂OCOC(CH₃)CH═CH₂) 49 ═C(CN)SO₂CH₃ 3-CH₃ —CH₂—C₆H₄-4-(CO₂—CH₂CH₂——CH₂—C₆H₄-4-(CO₂—CH₂CH₂— OCOC(CH₃)CH═CH₂) OCOC(CH₃)CH═CH₂) 50═C(CN)CO₂CH₃ 3-CH₃ —CH₂CH₂O-C₆H₃-3,5-bis- —C₂H₅ (—CO₂CH₂—C₆H₄-4-CH═CH₂)51 ═C(CN)CONH₂ 3-CH₃ —C₂H₅ —CH₂CH₂S—C₆H₄-2-(CO₂— CH₂—C₆H₄-4-CH═CH₂) 52═C(CN)CO₂C₂H₅ 3-CH₃ —CH₂C₆H₅ —CH₂—C₆H₄-4-(CO₂—CH₂— C₆H₄-4-CH═CH₂) 53═C(CN)CN 3-CH₃

—C₂H₅ 54 ═C(CN)CO₂CH₃ 3-CH₃ —CH₂CH₂S—C₆H₄-2-(CO₂— —CH₃CH₂—C₆H₄-4-CH═CH₂) 55 ═C(CN)CN 2,5-di-OCH₃ —CH₂—C₆H₄-4-(CO₂—CH₂CH₂——CH₂CH₂O—C₆H₄-2-(CO₂— OCOC(CH₃)CH═CH₂) CH₂CH₂—OCO—CH═CH₂) 56═C(CN)CO₂C₂H₅ H —CH₂CH₂—CO₂CH₂—C₆H₄- —CH₂CH₂—CO₂CH₂—C₆H₄- 4-CH═CH₂4-CH═CH₂

TABLE III 3-Aryl-2,5-Dioxypyrroline Colorants of Formula XVII

Example No. R₁₅ R₁₆ R₁₆′ R₁₇ 57 H —CH₂CH₃ H —CH₂—C₆H₄-4-(CO₂—CH₂CH₂—OCOC(CH3)═CH₂) 58 H —CH₂CH₃ —CH₃ —C₆H₄-4-(CO₂—CH₂—C₆H₄-4-CH═CH₂) 59 H—CH₂—C₆H₄-4-(CO₂—CH₂—C₆H₄- —C₂H₅ —CH₂—C₆H₄-4-(CO₂—CH₂—C₆H₄- 4-CH═CH₂)4-CH═CH₂) 60 H —CH₂CH₂S—C₆H₄-2-(CO₂—CH₂CH₂— —CH₂C₆H₅—CH₂CH₂S—C₆H₄-2-(CO₂—CH₂CH₂— OCOC(CH3)═CH₂) OCOC(CH3)═CH₂) 61 H—CH₂CH₂O—C₆H₃-3,5-bis-(—CO₂CH₂— H —C₂H₅ C₆H₄-4-CH═CH₂) 62 —CH₃—CH₂—C₆H₄-4-(CO₂—CH₂CH₂— R₁₆ —C₂H₅ OCOCH═CH₂)

TABLE IV ANTHRAQUINONE COLORANTS OF FORMULA XXa

Example No. R₂₈ L₄ X 63 H 1-NH— —CH₂—C₆H₄-4-CH═CH₂ 64 H 2,7-di-S——CH₂—C₆H₄-4-CH═CH₂ 65 H 1,5-di-NH— —CH₂—C₆H₄-4-CH═CH₂ 66 H 1,8-di-NH——CH₂—C₆H₄-4-CH═CH₂ 67 H 1,5-di-S— —CH₂—C₆H₄-4-CH═CH₂ 68 H 1,5-di-S——CH₂CH(CH₃)OCOC(CH₃)═CH₂ 69 H 1,5-di-NH— —CH₂—CH(OH)CH₂—OCONH—CH₂CH₂OCOCH═CH₂ 70 1-NH₂-2-Br 4-NH —CH₂—C₆H₄-4-C(CH₃)═CH₂ 711-NH₂-2-SO₂C₆H₅ 4-NH —CH₂CH(CH₃)OCOCH═CH₂ 72 1-NH₂-2-S—C₆H₅ 4-NH—CH₂CH₂CH₂OCOC(CH₃)═CH₂ 73 1-NH₂-2-CN 4-NH —(CH₂)₄—OCONHCOC(CH₃)═CH₂ 741-NHCH₃ 4-NH —CH₂C(CH₃)₂CH₂OCOC(CH₃)═CH₂ 75 1-NHCH₂CH(CH₃)₂ 4-S——CH₂—C₆H₁₀-4-(CH₂OCOC(CH₃)═CH₂) 76 1-NH₂-4-OH 2-O— —(CH₂)₄—OCOCH═CH₂ 77H 1,4-di-S— —CH₂-1,4-C₆H₄CH═CH₂ 78 1-NH₂-4-NHC₆H₅ 2-S——CH₂CH₂OCONHC(CH₃)₂—C₆H₄- 3-C(CH₃)═CH₂ 79 1-NH2, 4-S-benzo- 2-SO₂——CH₂-1,4-C₆H₄—CH═CH₂ thiazol-2-yl 80 1,5-di-S—C₆H₅ 4,8-di-S——CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 81 1,8-di-NH₂-4,5- 2,7-di-O——CH₂CH₂OCH₂CH₂OCOC(CH₃)═CH₂ di-OH 82 1,8-di-NH₂-4,5- di-OH 2,5-di-S—

83 1,8-di-OH 4,5-di-S— —CH₂CH₂(OCH₂CH₂)₃OCOC(CH₃)═CH₂

TABLE V Anthraquinone Colorants of Formula XXb

Example No. R₂₈ R₂₉ L₄ —CO₂X 84 H H 1-S— 2′-CO₂CH₂CH(CH₃)OCOC(CH₃)═CH₂85 H H 1,5-di-NH— 2′-CO₂CH₂CH(CH₃)OCOCH═CH₂ 86 H 4′-Br 1,5-di-NH—2′-CO₂CH₂CH(CH₃)OCONHC(CH₃)₂—C₆H₄- 3-C(CH₃)═CH₂ 87 H H 1,5-di-S—3′-CO₂CH₂CH₂OCOC(CH₃)═CH₂ 88 H H 1,8-di-S— 4′-CO₂CH₂CH₂CH₂OCOCH═CH—CO₂H89 H 2′-CH₃ 1,4-di-S— 4′-CO₂CH₂—C₆H₄-4-CH═CH₂ 90 H H 1,4,5,8-tetra-S—2′-CO₂CH₂CH(CH₃)OCOC(CH₃)═CH₂ 91 1,5-di-NH— H 4,8-di-S—2′-CO₂CH₂CH(CH₃)OCOC(CH₃)═CH₂ C₆H₁₁ 92 1-NH₂-2-Br H 4-NH—2′-CO₂CH₂CH₂OCONHCOC(CH₃)═CH₂ 93 1-NH₂-2-OCH₃ H 4-S—2′-CO₂CH₂—C₆H₄-4-C(CH₃)═CH₂ 94 1-NH₂-2- H 4-NH—2′-CO₂CH₂CH(CH₃)OCOC(CH₃)═CH₂ SO₂C₆H₅ 95 1-NH₂-4- H 2-O—4′CO₂CH₂CH(OH)CH₂OCOCH═CH₂ NHSO₂CH₃ 96 1-NH₂-2-CF₃ H 4-S—3′-CO₂CH₂—C₆H₄-4-CH═CH₂ 97 1,4-di-OH H 2-S— 2′-CO₂(CH₂)₆OCOC(CH₃)═CH₂ 981,8-di-NH₂-4,5- H 2,7-di-S— 2′-CO₂CH₂CH(CH₃)OCOC(CH₃)═CH₂ di-OH 995,8-di-S—C₆H₅ H 1,4-di-S— 2′CO₂CH₂CH(CH₃)OC-1,3-C₆H₄—CH═CH₂ 1001,4-bis-(2,6- H 6,7-di-S— 2′-CO₂CH₂CH(CH₃)OCOC(CH₃)═CH₂ diethylanhlino)

TABLE VI ANTHRAQUINONE COLORANTS OF FORMULA XXe

Example No. R₂₈ Position R Y 101 H 1- H —CH₂—C₆H₄-4-CH═CH₂ 102 H 1,8-diH —CH₂CH₂OCOC(CH₃)═CH₂ 103 H 1,4,5,8- H —CH₂CH₂OCOCH═CH₂ tetra 1044,5-bis-(—SC₆H₄-4- 1,8-di —CH₃ —CH₂CH₂OCOC(CH₃)═CH₂ CH₃) 105 H 1,5-di—C₆H₅ —CH₂CH(CH₃)OCOCH═CH₂ 106 1-NH₂-2-Br 4- H —CH₂—C₆H₄-4-CH═CH₂ 1071-NH₂ 2,4-di H —CH₂CH₂OCOC(CH₃)═CH₂ 108 1-NH₂-4-OH 2- H—CH₂CH₂OCONHC(CH₃)₂— C₆H₄-3-C(CH₃)═CH₂ 109 1,8-di-NH₂-4,5-di-OH 2,7-di H—CH₂CH₂OCOC(CH₃)═CH₂ 110 1,4-bis-(2,6-diethyl- 6,7-di H—(CH₂)₆—OCOC(CH₃)═CH₂ anilino) 111 1,4-bis-(2,4,6-tri- 6,7-di H—CONHCOC(CH₃)═CH₂ methylanilinoPosition of triazolylthio radical(s):

quinone nucleus of Formula XXe. TABLE VII Anthrapyridone Colorants ofFormula XXIa

Example No. R₂₈ R₃₀ R₃₁ L₄ X 112 H —CH₃ H -6-NH— —CH₂—C₆H₄-4-CH═CH₂ 113H —CH₃ H -6-NH— —CH₂CH₂OCOC(CH₃)═CH₂ 114 H —CH₃ H -6-NH——CH₂CH₂OCOCNHC(CH₃)₂—C₆H₄- 4-C(CH₃)═CH₂ 115 H —CH₃ —CN -6-NH——CH₂CH(CH₃)OCOC(CH₃)═CH₂ 116 H —CH₃ —CN -6-NH— —CH₂CH(OH)CH₂OCOCH═CH₂117 H —C₄H₉-n —CO₂C₂H₅ -6-NH— —CH₂—C₆H₄-4-CH═CH₂ 118 H —CH₃ —CO₂C₂H₅-6-NH— —CH₂CH₂OCONHCOC(CH₃)═CH₂ 119 4-Br H —CO₂C₂H₅ -6-NH——CH₂CH₂CH₂OCOC(CH₃)═CH₂ 120 4-SO₂C₆H₅ H —CO₂C₂H₅ -6-NH——CH₂—C₆H₄-4-CH═CH₂ 121 4-S—C₆H₅ H —CO₂C₂H₅ -6-NH—

122 4-CH₃ H —COCH₃ -6-NH— —CH₂CH₂OCH₂CH₂OCOCH═CH₂ 123 4-OC₆H₅ H —COC₆H₅-6-NH— —CH₂—C₆H₄-4-CH═CH₂ 124 H —CH₃ —CO₂C₂H₅ 4,6-di-S——CH₂—C₆H₄-4-CH═CH₂ 125 6-NHC₆H₅ —CH₃ —CO₂C₂H₅ 4-O— —CH₂—C₆H₄-4-CH═CH₂126 6-NHC₆H₅ —CH₃ —CO₂C₂H₅ 4-S— —CH₂CH₂OCOC(CH₃)═CH₂ 127 H —C₆H₅ —CN6-S— —CH₂CH₂OCNH(CH₂)₆— OCOC(CH₃)═CH₂

TABLE VIII Anthrapyridone Colorants of Formula XXIb

Example No. R₂₈ R₂₉ R₃₀ R₃₁ L₄ —CO₂X 128 H H —CH₃ H 6-NH—2′-CO₂CH₂—C₆H₄-4-CH═CH₂ 129 H H —CH₃ H 6-S— 2′-CO₂CH₂—C₆H₄-4-CH═CH₂ 130H 4′-Br —CH₃ H 6-NH— 2′-CO₂CH₂CH₂OCOC(CH₃)═CH₂ 131 H 2′-CH₃ —CH₃ H 6-NH—4′-CO₂CH₂CH(CH₃)— OCOC(CH₃)═CH₂ 132 H H —CH₃ —CO₂C₂H₅ 4-S—, 6-2′-CO₂CH₂CH₂OCH₂CH₂— NH— OCOCH═CH₂ 133 H H —CH₃ —CO₂C₂H₅ 6-S—4′-CO₂CH₂—C₆H₄-4-CH═CH₂ 134 4-Br H H —CO₂C₂H₅ 6-NH—3′-CO₂CH₂CH₂OCOC(CH₃)═CH₂ 135 4-SO₂— H H —CO₂C₂H₅ 6-NH—2′-CO₂CH₂—C₆H₁₀-4- CH₃ (CH₂OCOCH═CH₂) 136 4-S— H H —CO₂C₂H₅ 6-NH—2′-CO₂CH₂C(CH₃)₂CH₂— C₆H₁₁ OCOC(CH₃)═CH₂ 137 H H H 2-benzox- 6-NH—2′-CO₂CH₂CH₂OCOC(CH₃)═CH₂ azolyl 138 H H H 2-benzo- 6-NH—2′-CO₂CH₂CH₂OCOC(CH₃)═CH₂ thiazolyl 139 H H —C₆H₁₁ —SC₆H₅ 6-NH—2′-CO₂CH₂CH₂OCOC(CH₃)═CH₂ 140 H H —CH₂C₆H₅ —SO₂C₆H₅ 6-NH—2′-CO₂CH₂CH₂OCOC(CH₃)═CH₂ 141 H H —CH₂CH₂— —Cl 6-NH—2′-CO₂CH₂CH₂OCOC(CH₃)═CH₂ OCH₃

TABLE IX Anthrapyridine Colorants of Formula XXIIa

Example No. R₂₈ R₃₁ R₃₂ L₄ X 142 H —CN —N(CH₃)₂ 6-NH——CH₂1,4-C₆H₄—CH═CH₂ 143 H —CN —N(C₂H₅)₂ 6-NH— —CH₂CH₂OCOC(CH₃)═CH₂ 144 H—CN —N(CH₃)C₆H₅ 6-NH— —CH₂CH(CH₃)OCOCH═CH₂ 145 H —CN Piperidino 6-NH——CH₂CH₂OCNHC(CH₃)₂—C₆H₄- 3-C(CH₃)═CH₂ 146 H —CN Morpholino 6-NH——CH₂C(CH₃)₂CH₂OCOC (CH3)═CH2 147 H —CN Pyrrolidino 4-S—, 6-NH—CH₂CH₂OCO—C₆H₄-4-CH═CH₂ 148 H —CN —N(CH₂CH₂OCH₃)₂ 4-S—, 6-NH—CH₂CH₂OCOC(CH₃)₂— NHCOC(CH₃)═CH₂ 149 H —CN —N(CH₃)C₆H₁₁ 6-S——CH₂CH₂OCOCH═CH—CO₂H 150 H —CN —N(CH₃)C₂H₅ 4,6-di-S——(CH₂)₆OCOCH═CH—CO₂C₂H₅ 151 4-Br —CN —N(C₂H₅)C₆H₅ 6-NH—CH₂—C₆H₁₀-4-(CH₂OCO CH═CH₂) 152 4-SO₂— —CN —N(CH₃)₂ 6-NH—CH₂CH(OH)CH₂OCOCH═CH₂ C₆H₅ 153 4-CF₃ —CN —N(CH₃)₂ 6-NH—CH₂CH₂(OCH₂CH₂)₃OCOCH═CH₂ 154 H H H 6-NH —CH₂CH(CH₃)OCOC(CH₃)═CH₂ 155 HC₆H₅ CH₃ 6-NH —CH₂CH(CH₃)CH₂OCOCH═CH₂

TABLE X Anthrapyridine Colorants of Formula XXIIb

Example No. R₂₈ R₂₉ R₃₁ R₃₂ L₄ —CO₂X 156 H H —CN Piperidino -6-NH2′-CO₂CH₂-1,4-C₆H₄—CH═CH₂ 157 H 4′-Br —CN Morpholino -6-NH2′-CO₂CH₂CH₂OCOC(CH₃)═CH₂ 158 H 4′-CH₃ —CN Pyrrolidino -6-NH3′-CO₂CH₂CH(CH₃)OCOCH═CH₂ 159 H H —CN —N(CH₃)₂ -6-NH4′-CO₂(CH₂)₃OCOC(CH₃)═CH₂ 160 H H —CN —N(CH₃)C₆H₅ -4-S-6-2′-CO₂CH₂CH₂OCOC(CH₃)═CH₂ NH— 161 4-Br H —CN —N(CH₃)C₂H₅ 6-S—2′-CO₂CH₂-1,4-C₆H₄—CH═CH₂ 162 4-SO₂CH₃ H —CN —N(CH₃)C₆H₁₁ 4-SO₂-6-2′CO₂CH₂C(CH₃)₂CH2— NH— OCOC(CH₃)═CH₂ 163 4-CN H —CN —N(CH₂CH₂— 6-NH—3′-CO₂CH₂CH₂OCOCH═CH— OC₂H₅)₂ CO₂H 164 4-OCH₃ H —CN —N(C₂H₅)C₆H₅ 6-NH—4′-CO₂CH₂—C₆H₄-4-CH═CH₂ 165 6-NHC₆H₅ H —CN —N(C₂H₅)₂ 4-S—2′-CO₂CH₂—C₆H₄-4-C(CH₃)═CH₂ 166 4-SO₂— H —CN —N(C₂H₅)₂ 4-S—2′-CO₂CH₂—C₆H₄-4-C(CH₃)═CH₂ N(CH₃)₂ 167 4-CH₃ H —CN —N(C₂H₅)₂ 4-S—2′-CO₂CH₂—C₆H₁₀-4- (OCOC(CH₃)═CH₂) 168 H H —CO₂CH₃ —N(C₂H₅)₂ 6-NH—2′CO₂CH₂CH₂OCH₂CH₂— OCOCH═CH₂ 169 H H H —C₆H₅ 6-NH— 2′CO₂CH₂CH(OH)CH₂—OCOCH═CH₂ 170 H H —CH₃ H 6-NH— 2′CO₂CH₂CH(OH)CH₂— OCOCH═CH₂ 171 H H—C₆H₅ —CH₃ 6-NH— 2′CO₂CH₂CH(OH)CH₂— OCOCH═CH₂

TABLE XI Quinophthalone Colorants of Formula XXIII

Example No. R₃₅ X 172 H —CH₂CH₂OCOC(CH₃)═CH₂ 173 H—CH₂CH₂OCONHC(CH₃)₂—C₆H₄-3-C(CH₃)═CH₂ 174 H —CH₂CH(CH₃)OCOCH═CH₂ 175 H—CH₂CH(OH)CH₂OCOC(CH₃)═CH₂ 176 Br —CH₂CH₂OCOC(CH₃)═CH₂ 177 Br—CH₂CH₂OCONHC(CH₃)₂—C₆H₄-3-C(CH₃)═CH₂ 178 Br —CH₂—C₆H₄-4-CH═CH₂ 179—SO₂C₆H₅ —CH₂CH₂OCOC(CH₃)═CH₂ 180 —SO₂—C₆H₄-4-CH₃—CH₂CH₂OCONHCOC(CH₃)═CH₂ 181 —S—C₆H₄—CH₃ —CH₂C(CH₃)₂CH₂OCOC(CH₃)═CH₂ 1822-benzothiazolyl —CH₂—C₆H₁₀-4-(CH₂OCOC(CH₃)═CH₂) 183 2-benzoxazolyl—CH₂CH₂O—C₆H₄-4- (OCH₂CH₂OCOC(CH₃)═CH₂) 184 1,2,4-triazol-3-ylthio—CH₂—C₆H₄-4-(CH₂OCOCH═CH₂) 185 —S—C₆H₄-2-(CO₂CH₂CH₂OCOCH═CH₂)—CH₂CH₂OCOCH═CH₂

TABLE XII Nitroarylamine Colorants of Formula XXIV

Example No. R₃₆ R₃₇ R₃₈

CO₂X)₀₋₂ 186 H —CH₃ —CH₃ 4-CO₂CH₂CH₂OCOC(CH₃)═CH₂ 187 H —CH₂CH₃ —CH₂CH₃3-CO₂CH₂CH(CH₃)OCOCH═CH₂ 188 H —CH₂CH₃ —CH₃ 3,5-di—CO₂CH₂CH₂—OCOC(CH₃)═CH₂ 189 H —C₆H₅ —CH₃ 2,5-di—CO₂(CH₂)₆OCOC(CH₃)═CH₂ 190 H—C₄H₉-n H 2-CO₂CH₂—C₆H₄-4-CH═CH₂ 191 H —C₆H₁₁ H 2-CO₂CH₂CH₂OCONHC(CH₃)₂—C₆H₄-3-C(CH₃)═CH₂ 192 H —C₆H₅ H 2-CO₂CH₂CH₂OCOCH═CH—CO₂H 193 H—C₆H₄-2-(CO₂CH₂CH₂— H H OCOCH═CH₂) 194 H —C₆H₃-3,5-bis(CO₂CH₂— H HC₆H₄—CH═CH₂) 195 H —C₆H₄-2-(CO₂CH₂CH₂ H 2-(CO₂CH₂CH₂OCOC(CH₃)═CH₂)OCOC(CH₃)═CH₂)

TABLE XIII Diarylamino Terephthlate Colorants of Formula XXIX

Example No. R₄₀ X 196 H —CH₂C(CH₃)₂CH₂OCOC(CH₃)═CH₂ 197 H—CH₂—C₆H₁₀-4-(CH₂—OCOCH═CH₂) 198 H —CH₂CH₂(OCH₂CH₂)₂OCOC(CH₃)═CH₂ 199 H—CH₂CH(CH₃)OCOC(CH₃)═CH₂ 200 H —CH₂CH(OH)CH₂OCOCH═CH₂ 201 H—CH₂CH₂OCONHC(CH₃)₂—C₆H₄-3- C(CH₃)═CH₂ 202 H —CH₂CH₂OCONHCOC(CH₃)═CH₂203 4-CH₃ —CH₂CH₂OCOC(CH₃)═CH₂ 204 4-Cl —CH₂—C₆H₄-4-CH═CH₂ 205 4-Br—CH₂CH(CH₃)OCOCH═CH₂ 206 3-C₂H₅ —CH₂CH₂OCONH(CH₂)₆OCOC(CH₃)═CH₂ 2074-C₆H₅ —CH₂CH₂OCOCH═CH—C₆H₅ 208 2-CH₃ —CH₂CH₂OCOCH═CH—CH₃ 209 2,5-di-CH₃—CH₂CH₂OCOCH═CH—CO₂H 210 4-OC₂H₅ —CH₂CH₂OCOC(CH₃)₂NHCOC(CH₃)═CH₂

TABLE XIV Miscellaneous Colorants EXAMPLE 211

EXAMPLE 212

EXAMPLE 213

EXAMPLE 213

EXAMPLE 214

EXAMPLE 215 2(3), 16(17)-di-[CO₂CH₂CH₂—OCOC(CH₃)═CH₂]-PcCu Pc =phthalocyanine EXAMPLE 216 2(3), 9(10), 16(17),23(24)-Tetra[2′-CO₂CH₂CH₂—O—COC(CH₃)═CH₂)phenoxy]-PcCu Pc =Phthalocyanine

The functionalized dyes or colorants which contain vinyl or substitutedvinyl groups are polymerizable or copolymerizable, preferably by freeradical mechanisms, said free radicals being generated by exposure to UVlight by methods known in the art of preparing UV-cured resins.Polymerization can be facilitated by the addition of photoinitiators.The colored polymeric materials normally are prepared by dissolving thefunctionalized colorants containing copolymerizable groups in apolymerizable vinyl monomer with or without another solvent and thencombining with an oligomeric or polymeric material which contains one ormore vinyl or substituted vinyl groups.

The eighth embodiment of the present invention is a coating compositioncomprising (i) one or more polymerizable vinyl compounds, i.e., vinylcompounds which are copolymerizable with the dye compounds describedherein, (ii) one or more of the dye compounds described above, and (iii)at least one photoinitiator. The polymerizable vinyl compounds useful inthe present invention contain at least one unsaturated group capable ofundergoing polymerization upon exposure to UV radiation in the presenceof a photoinitiator, i.e., the coating compositions areradiation-curable. Examples of such polymerizable vinyl compoundsinclude acrylic acid, methacrylic acid and their anhydrides; crotonicacid; itaconic acid and its anhydride; cyanoacrylic acid and its esters;esters of acrylic and methacrylic acids such as allyl, methyl, ethyl,n-propyl, isopropyl, butyl, tetrahydrofurfuryl, cyclohexyl, isobornyl,n-hexyl, n-octyl, isooctyl, 2-ethylhexyl, lauryl, stearyl, and benzylacrylate and methacrylate; and diacrylate and dimethacrylate esters ofethylene and propylene glycols, 1,3-butylene glycol, 1,4-butanediol,diethylene and dipropylene glycols, triethylene and tripropyleneglycols, 1,6-hexanediol, neopentyl glycol, polyethylene glycol, andpolypropylene glycol, ethoxylated bisphenol A, ethoxylated andpropoxylated neopentyl glycol; triacrylate and trimethacrylate esters oftris-(2-hydroxyethyl)isocyanurate, trimethylolpropane, ethoxylated andpropoxylated trimethylolpropane, pentaerythritol, glycerol, ethoxylatedand propoxylated glycerol; tetraacrylate and tetramethacrylate esters ofpentaerythritol and ethoxylated and propoxylated pentaerythritol;acrylonitrile; vinyl acetate; vinyl toluene; styrene; N-vinylpyrrolidinone; alpha-methylstyrene; maleate/fumarate esters;maleic/fumaric acid; crotonate esters, and crotonic acid.

The polymerizable vinyl compounds useful in the present inventioninclude polymers which contain unsaturated groups capable of undergoingpolymerization upon exposure to UV radiation in the presence of aphotoinitiator. The preparation and application of these polymerizablevinyl compounds are well known to those skilled in the art as described,for example, in Chemistry and Technology of UV and EB Formulation forCoatings, Inks, and Paints, Volume II: Prepolymers and ReactiveDiluents, G. Webster, editor, John Wiley and Sons, London, 1997.Examples of such polymeric, polymerizable vinyl compounds includeacrylated and methacrylated polyesters, acrylated and methacrylatedpolyethers, acrylated and methacrylated epoxy polymers, acrylated ormethacrylated urethanes, acrylated or methacrylated polyacrylates(polymethacrylates), and unsaturated polyesters. The acrylated ormethacrylated polymers and oligomers typically are combined withmonomers which contain one or more acrylate or methacrylate groups,e.g., monomeric acrylate and methacrylate esters, and serve as reactivediluents. The unsaturated polyesters, which are prepared by standardpolycondensation techniques known in the art, are most often combinedwith either styrene or other monomers, which contain one or moreacrylate or methacrylate groups and serve as reactive diluents. A secondembodiment for the utilization of unsaturated polyesters that is knownto the art involves the combination of the unsaturated polyester withmonomers that contain two or more vinyl ether groups or two or morevinyl ester groups (WO 96/01283, WO 97/48744, and EP 0 322 808).

The coating compositions of the present invention optionally may containone or more added organic solvents if desired to facilitate applicationand coating of the compositions onto the surface of substrates. Typicalexamples of suitable solvents include, but are not limited to ketones,alcohols, esters, chlorinated hydrocarbons, glycol ethers, glycolesters, and mixtures thereof. Specific examples include, but are notlimited to acetone, 2-butanone, 2-pentanone, ethyl acetate, propylacetate, isopropyl acetate, butyl acetate, isobutyl acetate, ethyleneglycol diacetate, ethyl 3-ethoxypropionate, methyl alcohol, ethylalcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, ethyleneglycol, propylene glycol, ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, ethylene glycol monopropyl ether, ethyleneglycol monobutyl glycol, diethylene glycol monomethyl ether, diethyleneglycol monoethyl ether, diethylene glycol monobutyl ether, propyleneglycol monomethyl ether, diethylene glycol monobutyl ether acetate,diethylene glycol monoethyl ether acetate, ethylene glycol monobutylether acetate, propylene glycol monomethyl ether acetate, methylenechloride, chloroform, and mixtures thereof. The amount of added orextraneous solvent which may be present in our novel coatingcompositions may be in the range of about 1 to 70 weight percent, moretypically about 1 to 25 weight percent, based on the total weight of thecoating composition.

Certain polymerizable vinyl monomers may serve as both reactant andsolvent. These contain at least one unsaturated group capable ofundergoing polymerization upon exposure to UV radiation in the presenceof a photoinitiator. Specific examples include, but are not limited to:methacrylic acid, acrylic acid, ethyl acrylate and methacrylate, methylacrylate and methacrylate, hydroxyethyl acrylate and methacrylate,diethylene glycol diacrylate, trimethylolpropane triacrylate, 1,6hexanediol di(meth)acrylate, neopentyl glycol diacrylate andmethacrylate, vinyl ethers, divinyl ethers such as diethyleneglycoldivinyl ether, 1,6-hexanediol divinyl ether, cyclohexanedimethanoldivinyl ether, 1,4-butanediol divinyl ether, triethyleneglycol divinylether, trimethylolpropane divinyl ether, and neopentyl glycol divinylether, vinyl esters, divinyl esters such as divinyl adipate, divinylsuccinate, divilnyl glutarate, divinyl 1,4-cyclohexanedicarboxylate,divinyl 1,3-cyclohexanedicarboxylate, divinyl isophthalate, and divinylterephthalate, N-vinyl pyrrolidone, and mixtures thereof.

In addition, the compositions of the present invention may be dispersedin water rather than dissolved in a solvent to facilitate applicationand coating of the substrate surface. In the water-dispersedcompositions of the present invention a co-solvent is optionally used.Typical examples of suitable cosolvents include but are not limited toacetone, 2-butanone, methanol, ethanol, isopropyl alcohol, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, ethyleneglycol monopropyl ether, and ethylene glycol monobutyl ether, ethyleneglycol, and propylene glycol. Typical examples of water-solubleethylenically unsaturated solvents include but are not limited to:methacrylic acid, acrylic acid, N-vinyl pyrrolidone, 2-ethoxyethylacrylate and methacrylate, polyethylene glycol dimethacrylate,polypropylene glycol monoacrylate and monomethacrylate, and mixturesthereof. The amount of suitable aqueous organic solvent (i.e., organicsolvent and water) in the dispersed coating compositions of the presentinvention is about 10 to about 90 weight percent, preferably about 75 toabout 90 weight percent of the total coating composition.

The coating compositions of the present invention contain one or more ofthe reactive vinyl dye compounds described herein. The concentration ofthe dye compound or compounds may be from about 0.005 to 30.0,preferably from about 0.05 to 15.0, weight percent based on the weightof the polymerizable vinyl compound(s) present in the coatingcomposition, i.e., component (i) of the coating compositions. Thecoating compositions of the present invention normally contain aphotoinitiator. The amount of photoinitiator typically is about 1 to 15weight percent, preferably about 3 to about 5 weight percent, based onthe weight of the polymerizable vinyl compound(s) present in the coatingcomposition. Typical photoinitiators include benzoin and benzoin etherssuch as marketed under the tradenames ESACURE BO, EB1, EB3, and EB4 fromFratelli Lamberti; VICURE 10 and 30 from Stauffer; benzil ketals such as2,2-dimethoxy-1,2-diphenylethan-1-one (IRGACURE 651),2-hydroxy-2-methyl-1-phenylpropan-1-one (IRGACURE 1173),2-methyl-2-morpholino-1-(p-methylthiophenyl)propan-1-one (IRGACURE 907),alpha-hydroxyalkyl-phenones such as(1-hydroxycyclohexyl)(phenyl)methanone (IRGACURE 184),2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (IRGACURE369), 2-hydroxy-2-methyl-1-phenylpropan-1-one IRGACURE 1173) from CibaGeigy, Uvatone 8302 by Upjohn; alpha, alpha-dialkoxyacetophenonederivatives such as DEAP and UVATONE 8301 from Upjohn; DAROCUR 116,1173, and 2959 by Merck; and mixtures of benzophenone and tertiaryamines In pigmented coating compositions, the rate of cure can beimproved by the addition of a variety of phosphine oxide photoinitiaterssuch as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irganox 819),Irgacure 819, 1700, and 1700 and phosphine oxide mixtures such as a50/50 by weight mixtures of IRGACURE 1173 and2,4,6-trimethylbenzoyidiphenylphosphine oxide (DAROCUR 4265) from Ciba.Further details regarding such photoinitiators and curing procedures maybe found in the published literature such as U.S. Pat. No. 5,109,097,incorporated herein by reference. Depending upon the thickness of thecoating (film), product formulation, photoinitiator type, radiationflux, and source of radiation, exposure times to ultraviolet radiationof about 0.5 second to about 30 minutes (50-5000 mJ/square cm) typicallyare required for curing. Curing also can occur from solar radiation,i.e., sunshine.

The coating compositions of the present invention may contain one ormore additional components typically present in coating compositions.Examples of such additional components include leveling, rheology, andflow control agents such as silicones, fluorocarbons or cellulosics;flatting agents; pigment wetting and dispersing agents; surfactants;ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments;defoaming and antifoaming agents; anti-settling, anti-sag and bodyingagents; anti-skinning agents; anti-flooding and anti-floating agents;fungicides and mildewcides; corrosion inhibitors; thickening agents;and/or coalescing agents. The coating compositions of the presentinvention also may contain non-reactive modifying resins. Typicalnon-reactive modifying resins include homopolymers and copolymers ofacrylic and methacrylic acid; homopolymers and copolymers of alkylesters of acrylic and methacrylic acid such as methyl, ethyl, n-propyl,isopropyl, butyl, tetrahydrofurfuryl, cyclohexyl, isobornyl, n-hexyl,n-octyl, isooctyl, 2-ethylhexyl, lauryl, stearyl, and benzyl acrylateand methacrylate; acrylated and methacrylated urethane, epoxy, andpolyester resins, silicone acrylates, cellulose esters such as celluloseacetate butyrates, cellulose acetate, propionates, nitrocellulose,cellulose ethers such as methyl cellulose, ethyl cellulose,hydroxypropyl cellulose, and hydroxypropyl methyl cellulose.

Typical plasticizers include alkyl esters of phthalic acid such asdimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutylphthalate, and dioctyl phthalate; citrate esters such as triethylcitrate and tributyl citrate; triacetin and tripropionin; and glycerolmonoesters such as Eastman 18-04, 18-07, 18-92 and 18-99 from EastmanChemical Company. Specific examples of additional additives can be foundin Raw Materials Index, published by the National Paint & CoatingsAssociation, 1500 Rhode Island Avenue, N.W., Washington, D.C. 20005.

The ninth embodiment of the present invention pertains to a polymericcomposition, typically a polymeric coating, comprising a polymer of oneor more acrylic acid esters, one or more methacrylic acid esters and/orother polymerizable vinyl compounds, having copolymerized therein one ormore of the dye compounds described above. The colored polymericcompositions provided by our invention may be prepared from the coatingcompositions described above and typically contain from about 0.005 to30.0 weight percent, preferably from about 05 to 15.0 weight percent, ofthe reactive or polymerized residue of one or more of the vinyl dyecompounds described herein based on the weight of the composition orcoating. The novel polymeric coatings may have a thickness of about 2.5to 150 microns, more typically about 15 to 65 microns.

The polymeric coatings of the present invention typically have a solventresistance of at least 100 MEK double rubs using ASTM Procedure D-3732;preferably a solvent resistance of at least about 200 double rubs. Suchcoatings also typically have a pencil hardness of greater than or equalto F using ASTM Procedure D-3363; preferably a pencil hardness ofgreater than or equal to H. The coating compositions can be applied tosubstrates with conventional coating equipment. The coated substratesare then exposed to radiation such as ultraviolet light in air or innitrogen which gives a cured finish. Mercury vapor or Xenon lamps areapplicable for the curing process. The coatings of the present inventioncan also be cured by electron beam.

The radiation-curable coating compositions of this invention aresuitable as adhesives and coatings for such substrates as metals such asaluminum and steel, plastics, glass, wood, paper, and leather. On woodsubstrates the coating compositions may provide both overall transparentcolor and grain definition. Various aesthetically-appealing effects canbe achieved thereby. Due to reduced grain raising and higher filmthicknesses, the number of necessary sanding steps in producing afinished wood coating may be reduced when using the colored coatingcompositions of the invention rather than conventional stains. Coatingcompositions within the scope of our invention may be applied toautomotive base coats where they can provide variousaesthetically-appealing effects in combination with the base coats andcolor differences dependent on viewing angle (lower angles create longerpath lengths and thus higher observed color intensities). This mayprovide similar styling effects as currently are achieved with metalflake orientation in base coats.

Various additional pigments, plasticizers, and stabilizers may beincorporated to obtain certain desired characteristics in the finishedproducts. These are included in the scope of the invention.

Coating, Curing, and Testing Procedures:

Samples of formulations were used to coat glass plates using a knifeblade. The wet film thickness was about 15 to 75 microns (0.6 to 3.0mils). The solvent was evaporated to give a clear, somewhat tacky film.Prior to exposure to UV radiation, each film was readily soluble inorganic solvents.

The dried film on the glass plate was exposed to UV radiation from a 200watt per inch medium pressure mercury vapor lamp housed in an AmericanUltraviolet Company instrument using a belt speed of 25 ft. per minute.One to five passes under the lamp resulted in a crosslinked coating withmaximum hardness and solvent resistance.

Each cured coating (film) may be evaluated for Konig Pendulum Hardness(ASTM D4366 DIN 1522), solvent resistance by the methyl ethyl ketonedouble-rub test, and solubility in acetone before and after exposure toUV radiation. The damping time for Konig Pendulum Hardness on uncoatedglass is 250 seconds; coatings with hardness above 100 seconds aregenerally considered hard coatings. The methyl ethyl ketone (MEK) doublerub test is carried out in accordance with ASTM Procedure D-3732 bysaturating a piece of cheese cloth with methyl ethyl ketone, and withmoderate pressure, rubbing the coating back and forth. The number ofdouble rubs is counted until the coating is removed. The acetonesolubility test is carried out by immersing a dry, pre-weighed sample ofthe cured film in acetone for 48 hours at 25° C. The film is removed,dried for 16 hours at 60° C. in a forced-air oven, and reweighed. Theweight percent of the insoluble film remaining is calculated from thedata.

COATING EXAMPLES

The coatings and coating compositions provided by the present inventionand the preparation thereof are further illustrated by the followingexamples.

Example 217

A colored, photopolymerizable composition was prepared by thoroughlymixing 0.5 g the yellow dye of Example 7 with a coating compositionconsisting of 20 g Jagalux UV1500 polyester acrylate, 10 g of bisphenolA epoxy acrylate, 9 g dipropyleneglycol diacrylate (DPGDA), 7 gtrimethylolpropane triacrylate (TMPTA), and 4 g of Darocure 1173photoinitiator using a small Cowles mixer until the components werecompletely dispersed. The resulting coating composition containing 1% ofthe yellow dye was drawn down with a wire wound rod to provide a 25.4micron (1 mil) thick coating on an oak wood panel. This panel was passedthrough a UV cure machine at a speed of 6.1 meters per minute (20feet/minute) using a lamp with an intensity of 118.1 watts per cm (300watts per inch). The same coating solutions were applied to glass panelsand cured under the same conditions of exposure. Konig Pendulum Hardnessmeasurements (ASTM D4366 DIN 1522) were conducted on the coated glasspanels and indicated no significant loss of hardness due toincorporation of the dye; hardness was 86 Konig seconds compared with 82seconds for a reference coating, which contained no polymerizable dye.Adhesion of the coating to an oak wood panel was measured using thecrosshatch adhesion method according to ASTM method D 3359 (ISO 2409). Aright angle lattice pattern (6 lines in each direction) is cut into thecoating, penetrating to the substrate, creating 25 squares with eachside of the squares measuring 1 mm. A 2.5 cm (1 inch) wide piece of tapeis applied to the lattice, pressure is applied, and then the tape ispulled from the substrate. If the edges are smooth and none of thesquares are detached, the adhesion is 100% (ASTM rating 5B). On the woodpanel a 5B rating was achieved for both the reference and thedye-containing coatings. Chemical resistance was tested with MEK doublerubs on glass. Both the reference, which contained no polymerizable dye,and the coatings, which contained polymerizable dyes, withstood morethan 300 MEK double rubs. No dye color was observed on the whitecheesecloth of the MEK rub test, which is an indication that the dyescannot be extracted from the coatings with solvents and demonstratescomplete incorporation of the dye into the polymer matrix of the curedfilm.

Example 218

A colored, photopolymerizable composition was prepared by thoroughlymixing 0.5 g the red dye of Example 8b with a coating compositionconsisting of 20 g Jägalux UV1500 polyester acrylate, 10 g of bisphenolA epoxy acrylate, 9 g dipropyleneglycol diacrylate (DPGDA), 7 gtrimethylolpropane triacrylate (TM PTA), and 4 g of Darocure 1173photoinitiator in a small Cowles mixer until the components werecompletely dispersed. The resulting coating composition, which contained1% of the red dye, was drawn down with a wire wound rod to provide a25.4 micron (1 mil) thick coating on an oak wood panel. This panel waspassed through a UV cure machine at a speed of 6.1 meters per minute (20feet/minute) using a lamp with an intensity of 118.1 watts per cm (300watts per inch). The same coating solutions were applied to glass panelsand cured under the same conditions of exposure. Konig Pendulum Hardnessmeasurements conducted on the coated glass panels showed no significantloss of hardness due to incorporation of the dye; hardness was 76 Konigseconds compared with 82 seconds for a reference coating which containedno polymerizable dye.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

1. Photopolymerizable colorant compounds having formula I or II:

wherein A, is a mono-, di-, tri- or tetravalent chromophore; X is—R₁—O-Q or the phtopolymerizable group —CH₂—C₆H₄-p-C(R₂)═CH₂; Y is—R₁—O-Q, —CH₂—C₆H₄-p-C(R₂)═CH₂ or Q; R is hydrogen, C₁-C₆ alkyl, aryl orC₃-C₈ cycloalkyl; R₁ is C₂-C₈ alkylene, —(—CH₂CH₂O—)_(m)—CH₂CH₂— or1,4-cyclohexylenedimethylene; R₂ is hydrogen or C₁-C₆ alkyl; n is 1 to4; m is 1-3; Q is a photopolymerizable group selected from an organicradical having the formula:

wherein R₃ is hydrogen or C₁-C₆ alkyl; R₄ is hydrogen; C₁-C₆ alkyl;phenyl; phenyl substituted with one or more groups selected from C₁-C₆alkyl, C₁-C₆ alkoxy, —N(C₁-C₆ alkyl)₂, nitro, cyano, C₂-C₆alkoxycarbonyl, C₂-C₆ alkanoyloxy and halogen; 1- or 2-naphthyl; 1- or2-naphthyl substituted with C₁-C₆ alkyl or C₁-C₆ alkoxy; 2- or3-thienyl; 2- or 3-thienyl substituted with C₁-C₆ alkyl or halogen; 2-or 3-furyl; or 2- or 3-furyl substituted with C₁-C₆ alkyl; R₅ and R₆ areindependently selected from hydrogen, C₁-C₆ alkyl, substituted C₁-C₆alkyl; or aryl; or R₅ and R₆ may be combined to represent a —(—CH₂—)₃₋₅—radical; R₇ is hydrogen or C₁-C₆ alkyl, substituted C₁-C₆ alkyl, C₃-C₈alkenyl, C₃-C₈ cycloalkyl or aryl; and R₈ is hydrogen, C₁-C₆ alkyl oraryl; and wherein A is an azo or bis-azo residue.
 2. (canceled) 3.Photopolymerizable colorant compounds according to claim 1 wherein X andY, respectively, are selected from —CH₂CH₂OQ, —CH₂CH(CH₃)OQ,—(CH₂CH₂O)₁₋₂—CH₂CH₂OQ, —CH₂C(CH₃)₂CH₂OQ, or —CH₂—C₆H₁₀—CH₂OQ. 4.Photopolymerizable colorant compounds according to claim 1 wherein Q is—COCH═CH₂ or —COC(CH₃)═CH₂.
 5. Photopolymerizable colorant compoundsaccording to claim 1 wherein X is —CH₂—C₆H₄-4-C(R₂)═CH₂ wherein R₂ ishydrogen or methyl; or —R₁—O-Q wherein R₁ is —(CH₂)₂₋₄—, —CH₂CH(CH₃)—,—CH₂C(CH₃)₂CH₂—, —(CH₂CH₂O—)₁₋₂CH₂CH₂—, —CH₂CH(OH)CH₂—, orCH₂—C₆H₁₀-4-CH₂—; and Q is —COC(R₃)═CH₂ wherein R₃ is hydrogen ormethyl; or —CONHC(CH₃)₂—C₆H₄-4-C(CH₃)═CH₂.
 6. Process for thepreparation of the photopolymerizable colorants defined in claim 1having Formula I wherein X is a p-vinylbenzyl radical having the formula—CH₂—C₆H₄-p-C(R₂)═CH₂ which comprises reacting colored acidic compoundshaving the structure:

with a compound having the structure ClCH₂—C₆H₄-p-C(R₂)═CH₂ in thepresence of base.
 7. Process for the preparation of thephotopolymerization colorants defined in claim 1 having Formula IIwherein Y is a p-vinylbenzyl radical having the formula—CH₂—C₆H₄-p-C(R₂)═CH₂ which comprises reacting colored acidic compoundshaving the structure

with 4-chloromethylstyrene compounds having the structureClCH₂₋C₆H₄₋p-C(R₂)═CH₂ in the presence of a base.
 8. Process for thepreparation of the photopolymerizable colorant compounds defined inclaim 1 having Formula I or Formula II wherein X or Y, respectively, is—CH₂CH₂—O-Q or —CH₂CH(CH₃)—O-Q, which comprises the steps of: (a)reacting colored acidic compounds having the structure:

with at least about n molecular equivalents of ethylene or propylenecarbonate for each molecular equivalent of acidic compound to producethe 2-hydroxyalkyl derivatives of said acidic compound; (b) reactingsaid colored 2-hydroxyalkyl derivatives with about n molecularequivalents of one or more acylating agents having the structures:ClCOC(R₃)═CH—R₄ or O[COC(R₃)═CH—R₄]₂,  IbO═C═N—COC(R₃)═CH—R₄,  IIbO═C═N—C₁-C₆ alkylene OCOC(R₃)═CH—R₄,  IIIb


9. Process according to claim 8 for the preparation of the coloredphotopolymerizable compounds having Formula II wherein Y is aphotopolymerizable group Q which comprises reacting a colored acidiccompound having the structure:

with at least about n molecular equivalents of an acylating agentselected from acylating agents Ib through IXb of.
 10. Process accordingto claim 8 for the preparation of the colored photopolymerizablecompounds having Formula II wherein Y is a photopolymerizable group Qwhich comprises the steps of: (a) reacting a colored acidictriazolylthio compound having the structure:

with at least about n molecular equivalents of ethylene or propylenecarbonate to produce a hydroxyalkyl compound having the formula

wherein R′ is hydrogen or methyl, and (b) reacting the hydroxyalkylcompund produced in step (a) with an acylating agent selected fromacylating agents Ib through IXb.
 11. A photopolymerizable azo colorantcompound defined in claim 5 having the formula

wherein D is an aryl or heteroaryl diazo group wherein the aryl orheteroaryl groups are unsubstituted or substituted with C₁-C₆ alkyl,C₁-C₆ alkoxy, C₁-C₆ alkylthio, halogen, C₂-C₆ alkoxycarbonyl, formyl,C₂-C₆ alkanoyl, dicyanovinyl, trifluoromethyl, cyano, carbamoyl,—CONH—C₁-C₆ alkyl, sulfamoyl, —SO₂NH—C₁-C₆ alkyl, phenylazo,phenylsulfonyl, fluorosulfonyl, benzoyl, C₁-C₆ alkylsulfonyl, nitro,—CO₂X or

wherein L is a linking group selected from —O—, —S— and —SO₂—; R₁₅ ishydrogen or 1 or 2 groups selected from C₁-C₆ alkyl; C₁-C₆ alkoxy;halogen; —NHCOR₂₂, —NHCO₂R₂₂, and —NHSO₂R₂₃ wherein R₂₂ is hydrogen,C₁-C₆ alkyl, or aryl and R₂₃ is C₁-C₆ alkyl, or aryl; wherein the C₁-C₆alkyl groups represented by R₂₂ and R₂₃ may be substituted with C₁-C₆alkoxy, aryl, cyano, halogen, C₂-C₆ alkanoyloxy, —CO₂X or

wherein L₁ is selected from a covalent bond, —O—, —S—, —SO₂—, —SO₂NH—and —CONH—; R₁₆ and R₁₇ are independently selected from hydrogen, C₁-C₆alkyl, cyclohexyl, aryl, and C₁-C₆ alkyl substituted with 1 or 2 groupsselected from aryl, C₁-C₆ alkoxy, cyano, —OCO—C₁-C₆-alkyl, halogen,succinimido, phthalimido, —CO₂X,

12-20. (canceled)